Flavoring agents containing bio-derived 1,3-propanediol and its conjugate esters

ABSTRACT

Biodegradable flavoring agent compositions comprising 1,3-propanediol are provided, and the 1,3-propanediol in the composition is biologically derived. The compositions exhibit a lower anthropogenic CO 2  emission profile. Also provided are biodegradable flavoring agent compositions comprising an ester of 1,3-propanediol. In these compositions, the ester can have at least 3% biobased carbon.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. patent application Ser. No.13/238,776, filed Sep. 21, 2011, now U.S. Pat. No. 8,436,046 which is aContinuation of U.S. patent application Ser. No. 12/786,506, filed onMay 25, 2010, now U.S. Pat. No. 8,048,920 which is a Continuation ofU.S. patent application Ser. No. 11/705,198, filed on Feb. 12, 2007, nowU.S. Pat. No. 7,759,393, which claims the benefit of U.S. ProvisionalApplication Ser. No. 60/772,471, filed Feb. 10, 2006, now expired; U.S.Provisional Application No. 60/772,194, filed Feb. 10, 2006, nowexpired, U.S. Provisional Application No. 60/772,193, filed Feb. 10,2006, now expired, U.S. Provisional Application No. 60/772,111, filedFeb. 10, 2006, now expired, U.S. Provisional Application No. 60/772,120,filed Feb. 10, 2006, now expired, U.S. Provisional Application No.60/772,110, filed Feb. 10, 2006, now expired, U.S. ProvisionalApplication No. 60/772,112, filed Feb. 10, 2006, now expired, U.S.Provisional Application No. 60/846,948, filed Sep. 25, 2006, nowexpired, U.S. Provisional Application No. 60/853,920, filed Oct. 24,2006, now expired, U.S. Provisional Application No. 60/859,264, filedNov. 15, 2006, now expired, U.S. Provisional Application No. 60/872,705,filed Dec. 4, 2006, now expired and U.S. Provisional Application No.60/880,824, filed Jan. 17, 2007, now expired, the disclosures of whichare expressly incorporated herein by reference in their entireties.

FIELD OF THE INVENTION

The invention relates to biodegradable flavoring agent compositionscomprising 1,3-propanediol, 1,3-propanediol ester, or combinationsthereof.

BACKGROUND OF THE INVENTION

Consumers and manufacturers are increasingly concerned with theenvironmental impact of all products. The effort towards environmentalimpact awareness is a universal concern, recognized by governmentagencies. The Kyoto Protocol amendment to the United Nations FrameworkConvention on Climate Change (UNFCCC) currently signed by 156 nations isone example of a global effort to favor safer environmentalmanufacturing over cost and efficiency. Especially when applied to goodslike, personal care, cosmetics, therapeutics and cosmeceuticals,consumers are increasingly selective about the origins of the productsthey purchase. The 2004 Co-operative Bank's annual Ethical ConsumerismReport (www.co-operativebank.co.uk) disclosed a 30.3% increase inconsumer spending on ethical retail products (a general classificationfor environmental safe, organic and fair trade goods) between 2003 and2004, while total consumer spending during the same period rose only3.7%.

One of the single greatest environmental concerns to consumers is theglobal warming effect and greenhouse gases that contribute to theeffect. Greenhouse gases are gases that allow sunlight to enter theatmosphere freely. When sunlight strikes the Earth's surface, some of itis reflected back towards space as infrared radiation. Greenhouse gasesabsorb this infrared radiation and trap the heat in the atmosphere. Overtime, the amount of energy sent from the sun to the Earth's surfaceshould be about the same as the amount of energy radiated back intospace, leaving the temperature of the Earth's surface roughly constant.However, increasing the quantity of greenhouse gases above the quantitythat existed before the rise of human industrialization is thought toincrease the retained heat on the Earth's surface and produce the globalwarming observed in the last two centuries.

Carbon dioxide is singled out as the largest component of the collectionof greenhouse gases in the atmosphere. The level of atmospheric carbondioxide has increased 50% in the last two hundred years. Any furtheraddition of carbon dioxide to the atmosphere is thought to further shiftthe effect of greenhouse gases from stabilization of global temperaturesto that of heating. Consumers and environmental protection groups alikehave identified industrial release of carbon into the atmosphere as thesource of carbon causing the greenhouse effect. Only organic productscomposed of carbon molecules from renewably based sources such as plantsugars and starches and ultimately atmospheric carbon are considered tonot further contribute to the greenhouse effect, when compared to thesame organic molecules that are petroleum or fossil fuel based.

In addition to adding carbon dioxide to the atmosphere, current methodsof industrial production of propanediols produce contaminants and wasteproducts that include among them sulfuric acid, hydrochloric acid,hydrofluoric acid, phosphoric acid, tartaric acid, acetic acids, Alkalimetals, alkaline earth metals, transitional metals and heavy metals,including Iron, cobalt, nickel, copper, silver, molybdenum, tungsten,vanadium, chromium, rhodium, palladium, osmium, iridium, rubidium, andplatinum (U.S. Pat. Nos. 2,434,110, 5,034,134, 5,334,778, and 5,10,036).

There is a need for all manufactures to provide products reducedenvironmental impacts, and to especially consider the carbon load on theatmosphere. There is also an environmental advantage for manufacturersto provide products of renewably based sources. Further, there is a needfor a proven solvent which is produced with no or little increase to thepresent carbon-dioxide level in the environment.

Published U.S. Patent Application No. 2005/0069997 discloses a processfor purifying 1,3-propanediol from the fermentation broth of a culturedE. coli that has been bioengineered to synthesize 1,3-propanediol fromsugar. The basic process entails filtration, ion exchange anddistillation of the fermentation broth product stream, preferablyincluding chemical reduction of the product during the distillationprocedure. Also provided are highly purified compositions of1,3-propanediol.

Personal care, animal care, cosmetic, therapeutic, pharmaceutic,nutraceutic, aromatherapy, fragrance and cosmeceutic formulationsbenefit from glycols in the compositions as, for example, surfactants,humectants, solvents, neutralizers, emulsifiers, preservatives and/orfragrance enhancers and fixatives. Typically the glycol component inpersonal care applications include propylene glycol, 1,3-butyleneglycol, or 2-methyl-1,3-propanediol. Because of production costs andrelative low purity, conventional 1,3-propanediol, though exhibitingproperties equal to if not better than the aforementioned glycols,generally is not used in such compositions.

Moreover, in the context of personal care, animal care, cosmetic,therapeutic, pharmaceutic, nutraceutic, aromatherapy, fragrance andcosmeceutic formulations incorporating a botanical, vegetal,protein/peptide, marine, algae or milk extract, or fragrance concentrateor oil, consumers pay attention to the quality and environmental impactof the product. Currently, botanical, vegetal, protein/peptide, marine,algae and milk extracts, and fragrance concentrates utilize chemicalsolvents, such as propylene glycol, 2-methyl-1,3-propanediol, butyleneglycol, dipropylene glycol, synthetic glycerin, and ethanol, for theextraction process. In many cases these chemical solvents are used incombination with each other. Despite the fact these chemicals aresuitable solvents, they have an intrinsic disadvantage because theyrepresent a petroleum-based component of an otherwise “all natural”product. Additionally, safety assessments of these solvents provideevidence that they can cause skin irritation. (Cosmetic IngredientReview Expert Panel (1994) Final Report on the Safety Assessment ofPropylene Glycol and Polypropylene Glycols. J. Am. College Toxicol.,13(6):437-491).

Essential oils extracted from plants are widely used cosmetic andpersonal care formulations. Colors extracted from plants are used in thefood and non-food-industry. Medicinal plant extractions are being usedfor the treatment various disorders. Though several methods can be usedfor extraction of flavors, fragrances, colors, and active ingredients,solvent extraction is one of widely used method. Selective extraction ofrequired ingredients, stability of the extracted ingredients, andseparation of ingredients from unwanted solvents are key factors forextraction. When volatile solvents such as ethanol used for extractionof active ingredients, they need to be removed before using theingredients in formulations. When solvents are removed some of theactive ingredients may not be stable and decompose.

SUMMARY OF THE INVENTION

Detergent compositions comprising 1,3-propanediol are provided, and the1,3-propanediol in the composition is biologically derived. Alsoprovided are detergent compositions comprising an ester of1,3-propanediol. In these compositions, the ester can have at least 3%biobased carbon.

DETAILED DESCRIPTION

Applicants specifically incorporate the entire content of all citedreferences in this disclosure. Further, when an amount, concentration,or other value or parameter is given as either a range, preferred range,or a list of upper preferable values and lower preferable values, thisis to be understood as specifically disclosing all ranges formed fromany pair of any upper range limit or preferred value and any lower rangelimit or preferred value, regardless of whether ranges are separatelydisclosed. Where a range of numerical values is recited herein, unlessotherwise stated, the range is intended to include the endpointsthereof, and all integers and fractions within the range. It is notintended that the scope of the invention be limited to the specificvalues recited when defining a range.

Solvents for diluting and extracting natural extracts are oftensynthetic, petroleum based organic solvents. Botanical, vegetal,protein/peptide, marine, algae, and milk extracts, also known as anessential oils, are an attractive component in many compositions. Theseessential oils impart aromatics, active ingredients, and otherfunctionalities such as hand-feel, softening, emoillency, healing,cooling, refreshing, antimicrobial, astringency, nail-strengthening,promotion of healthy skin tissue and hair, cleansing, stimulating,whitening, delivery of anti-oxidants and skin-soothing attributes to aproduct. Essential oils are the volatile oils of plant/vegetal,protein/peptide, lipid, marine, algae or milk materials that have beenremoved either by distillation or solvent extraction.

Biologically-derived 1,3-propanediol and its conjugate esters can beused as a solvent to extract essential oils and other extracts fromextract sources. Bio-derived 1,3-propanediol and its conjugate esterscan be used as a solvent system for botanical extracts and fragranceconcentrates and oils at a 10% to approaching 100% concentration range.

Additionally, biologically-derived 1,3-propanediol and its conjugateesters can be used as a solvent to dilute or solubilize extracts incompositions. Biologically-derived 1,3-propanediol and its conjugateesters are unique as solvents in that they are naturally derived, andtherefore attractive to consumers who avoid synthetic chemicals.

Biologically-derived 1,3-propanediol and its conjugate esters providefor non-irritating solvents for the extraction and dilution ofbotanicals, vegetal, protein/peptide, marine, algae, milk substrates orfragrance concentrates and oils. In an aspect of the invention thesolvent is composed of all natural components, the term “all natural” asused herein refers to a product that is manufactured from ingredientsthat are natural occurring. Specifically, biologically derived1,3-propanediol comprises non-petroleum based carbon.

The conjugate esters of biologically-derived 1,3-propanediol discussedherein include the mono and diesters of biologically derived1,3-propanediol.

Biologically-derived 1,3-propanediol or its ester conjugates areemployed as chemical solvents for extraction or diluent of a botanicalextract or fragrance concentrate or oil. The process of extracting anextract from a source comprises: (a) providing 1,3-propanediol, an esterof 1,3-propanediol, or a mixture thereof; (b) mixing the1,3-propanediol, the ester of 1,3-propanediol, or the mixture thereofwith the source, which extracts the extract from the source into theester; and (c) separating the source from the extract and1,3-propanediol, the ester of 1,3-propanediol, or the mixture thereof.

The process of extraction involves use of a dried substrate such asplant material which is macerated with solvent. Maceration is the mostcommon and economically important technique for extracting aromatics inthe modern perfume industry. In this method, raw materials are submergedin a solvent that can dissolve the desired aromatic or other extractcompounds. Maceration lasts between fractions of an hour to months.Maceration is often used to extract fragrant compounds from woody orfibrous materials, as well as animal sources. This technique is alsouseful to extract odorants that are too volatile for distillation oreasily denatured by heat.

Alternatively the solvent can be percolated though the substratematerial until sufficient soluble materials have leached from thebiomass or substrate. The substrate debris is separated from the extractby straining, filtering, or centrifugation.

Another technique for extracting compounds from a raw material issupercritical fluid extraction. This technique uses low heat to reducedegradation of the extract compounds. Supercritical CO2 can be used inthis extraction technique.

Extraction can be performed in accordance with the invention by otherextraction techniques as well, including distillation.Biologically-derived 1,3-propanediol and its conjugate esters can beused as solvents in distillation extractions. In this technique,commonly used to obtain aromatic compounds from plants, such as orangeblossoms and roses, the raw material is heated and the fragrantcompounds are recollected through condensation of the distilled vapor.Distillation methods include steam distillation, in which steam is usedto drive out volatile fragrant compounds from plant material, leaving acondensate which is called a hydrosol. Distillation also includes dry ordestructive distillation where the raw material is heated without acarrier solvent. In this case, biologically-derived 1,3-propanediol andits conjugate esters are used as a solvent to dilute the fragrantcompounds after extraction.

In yet another method of extraction, known as expression, raw materialis physically squeezed or compressed and the extruded oils arecollected. This method is known as extraction and is most commonlyperformed to extract compounds from the peels of fruits in the citrusfamily, as these sources contain sufficient oils to make this methodfeasible. Enfleurage is another extraction method appropriate for usewith biologically derived 1,3-propanediol, its conjugate esters, ormixtures thereof.

Biologically derived 1,3-propanediol and its conjugate esters are usefulas a solvents for extractions, and as a component in compositionscomprising botanical extracts. Botanical sources include, but are notlimited to all plants, seeds, stems, roots, flowers, leaves, pollen,spices, and oils. One type of extract appropriate for extraction ordilution is the herbal extract.

An herbal extract is a liquid solution of herbs and solvent. The driedor fresh herbs are combined with solvent, then the solid matter isremoved leaving only the oils of the herbs mixed with the solvent. Thisprocess is called extraction, and the process produces an herbalextract.

Herbal extracts are sold as dietary supplements and alternative medicineand commonly used for flavoring in baking, cooking or in beverages. Theyare also used in personal care products such as skin and hair products.

A small amount of the carbon dioxide in the atmosphere is radioactive.This 14C carbon dioxide is created when nitrogen is struck by anultra-violet light produced neutron, causing the nitrogen to lose aproton and form carbon of molecular weight 14 which is immediatelyoxidized in carbon dioxide. This radioactive isotope represents a smallbut measurable fraction of atmospheric carbon. Atmospheric carbondioxide is cycled by green plants to make organic molecules during theprocess known as photosynthesis. The cycle is completed when the greenplants or other forms of life metabolize the organic molecules producingcarbon dioxide which is released back to the atmosphere. Virtually allforms of life on Earth depend on this green plant production of organicmolecule to produce the chemical energy that facilitates growth andreproduction. Therefore, the 14C that exists in the atmosphere becomespart of all life forms, and their biological products. These renewablybased organic molecules that biodegrade to CO2 do not contribute toglobal warming as there is no net increase of carbon emitted to theatmosphere. In contrast, fossil fuel based carbon does not have thesignature radiocarbon ratio of atmospheric carbon dioxide.

Assessment of the renewably based carbon in a material can be performedthrough standard test methods. Using radiocarbon and isotope ratio massspectrometry analysis, the biobased content of materials can bedetermined. ASTM International, formally known as the American Societyfor Testing and Materials, has established a standard method forassessing the biobased content of materials. The ASTM method isdesignated ASTM-D6866.

The application of ASTM-D6866 to derive a “biobased content” is built onthe same concepts as radiocarbon dating, but without use of the ageequations. The analysis is performed by deriving a ratio of the amountof radiocarbon (14C) in an unknown sample to that of a modem referencestandard. The ratio is reported as a percentage with the units “pMC”(percent modern carbon). If the material being analyzed is a mixture ofpresent day radiocarbon and fossil carbon (containing no radiocarbon),then the pMC value obtained correlates directly to the amount of Biomassmaterial present in the sample.

The modern reference standard used in radiocarbon dating is a NIST(National Institute of Standards and Technology) standard with a knownradiocarbon content equivalent approximately to the year AD 1950. AD1950 was chosen since it represented a time prior to thermo-nuclearweapons testing which introduced large amounts of excess radiocarboninto the atmosphere with each explosion (termed “bomb carbon”). The AD1950 reference represents 100 pMC.

“Bomb carbon” in the atmosphere reached almost twice normal levels in1963 at the peak of testing and prior to the treaty halting the testing.Its distribution within the atmosphere has been approximated since itsappearance, showing values that are greater than 100 pMC for plants andanimals living since AD 1950. It's gradually decreased over time withtoday's value being near 107.5 pMC. This means that a fresh biomassmaterial such as corn could give a radiocarbon signature near 107.5 pMC.

Combining fossil carbon with present day carbon into a material willresult in a dilution of the present day pMC content. By presuming 107.5pMC represents present day biomass materials and 0 pMC representspetroleum derivatives, the measured pMC value for that material willreflect the proportions of the two component types. A material derived100% from present day soybeans would give a radiocarbon signature near107.5 pMC. If that material was diluted with 50% petroleum derivatives,it would give a radiocarbon signature near 54 pMC.

A biomass content result is derived by assigning 100% equal to 107.5 pMCand 0% equal to 0 pMC. In this regard, a sample measuring 99 pMC willgive an equivalent biobased content result of 93%.

Assessment of the materials described herein were done in accordancewith ASTM-D6866. The mean values quoted in this report encompasses anabsolute range of 6% (plus and minus 3% on either side of the biobasedcontent value) to account for variations in end-component radiocarbonsignatures. It is presumed that all materials are present day or fossilin origin and that the desired result is the amount of biobasedcomponent “present” in the material, not the amount of biobased material“used” in the manufacturing process.

“Substantially purified,” as used by applicants to describe thebiologically-produced 1,3-propanediol produced by the process of theinvention, denotes a composition comprising 1,3-propanediol having atleast one of the following characteristics: 1) an ultraviolet absorptionat 220 nm of less than about 0.200 and at 250 nm of less than about0.075 and at 275 nm of less than about 0.075; or 2) a composition havingL*a*b* “b*” color value of less than about 0.15 and an absorbance at 270nm of less than about 0.075; or 3) a peroxide composition of less thanabout 10 ppm; or 4) a concentration of total organic impurities of lessthan about 400 ppm.

A “b*” value is the spectrophotometrically determined “Yellow Bluemeasurement as defined by the CIE L*a*b* measurement ASTM D6290.

The abbreviation “AMS” refers to accelerator mass spectrometry.

The abbreviation “IRMS” refers to measurements of CO₂ by high precisionstable isotope ratio mass spectrometry.

“Biologically produced” means organic compounds produced by one or morespecies or strains of living organisms, including particularly strainsof bacteria, yeast, fungus and other microbes. “Bio-produced,”“biologically-derived” and “biologically produced” are used synonymouslyherein. Such organic compounds are composed of carbon from atmosphericcarbon dioxide converted to sugars and starches by green plants.

“Biologically-based” means that the organic compound is synthesized frombiologically produced organic components. It is further contemplatedthat the synthesis process disclosed herein is capable of effectivelysynthesizing other monoesters and diesters from bio-produced alcoholsother than 1,3-propanediol; particularly including ethylene glycol,diethylene glycol, triethylene glycol, −, dipropylene diol, tripropylenediol, 2-methyl 1,3-propanediol, neopentyl glycol and bisphenol A.“Bio-based”, and “bio-sourced”; “biologically derived”; and“bio-derived” are used synonymously herein.

“Carbon of atmospheric origin” as used herein refers to carbon atomsfrom carbon dioxide molecules that have recently, in the last fewdecades, been free in the earth's atmosphere. Such carbons in mass areidentifiable by the present of particular radioisotopes as describedherein. “Green carbon”, “atmospheric carbon”, “environmentally friendlycarbon”, “life-cycle carbon”, “non-fossil fuel based carbon”,“non-petroleum based carbon”, “carbon of atmospheric origin”, and“biobased carbon” are used synonymously herein.

“Flavoring agents” are substances added to foods, beverages, cosmetics,pharmaceuticals, or medicines to improve the quality of the taste ifsuch compositions. Oils, such as orange oils are considered flavoringagents.

An aspect of the invention is use of biologically-derived1,3-propanediol or its ester conjugate to prepare a flavoring agent, forexample by treating a flavoring oil with biologically-derived1,3-propanediol or its ester conjugate.

Compositions in accordance with the invention include a compositioncomprising an ester of 1,3-propanediol and an extraction product. Theesters can be a varying amount of biobased carbon depending on thecompound used in the esterification. Biologically derived1,3-propanediol contains biobased carbon. All three carbon atoms in 1,3propanediol are biobased carbons. If the conjugate esters are formedusing carboxylic acids that contain all biobased carbon, then theresulting esters also contain all biobased carbon. If, however, thecarboxylic acids contain non-biobased carbons, i.e. carbons from afossil fuel source, then the resulting ester will contain a percentageof biobased carbon in proportion to the number of carbons contributedfrom the carboxylic acid compared to the three carbons contributed fromthe biologically-derived 1,3-propanediol.

For example, distearate propanediol contains 39 carbon atoms, 18 fromeach of the stearic acid carbon chains and three from the1,3-propanediol. Accordingly, if the strearic acid is non-biobased, 36carbons out of the total 39 in distearate propanediol are non-biobasedcarbon. The predicted biobased content of distearate propanediol madefrom biologically-derived propanediol, and non-biologically derivedstrearic acid is 7.7 percent.

In an analysis performed using the ASTM-D6866 method, propylene glycoldibenzoate (BENZOFLEX (R) 284, Velsicol Chem. Corp. Rosemont, Ill.) wasfound to have 0% bio-based carbon content. The same analysis ofpropanediol dibenzoate, synthesized using biologically-derived1,3-propanediol had 19% bio-based carbon content. The predictedbio-based carbon content propanediol dibenzoate made frombiologically-derived 1,3 propanediol is 17.6%, which is within thestandard deviation of the method.

If the stearic acid in the above example is biobased, the resultingdistearate propanediol would have a biobased content of 100%.Accordingly, the conjugate esters of biologically-derived1,3-propanediol have biobased content values proportional to thebiobased content of the acids used to form the esters. The esterstherefore can have biobased content of at least 3% biobased carbon, atleast 6% biobased carbon, at least 10% biobased carbon, at least 25%biobased carbon, at least 50% biobased carbon, at least 75% biobasedcarbon, and 100% biobased carbon.

The compositions comprising an extract and a conjugate ester of1,3-propanediol can be between about 0.1% and about 5% ester, betweenabout 0.5% and about 25% ester, between about 25% and about 50% ester,between about 50% and about 75% ester, and between about 75% and about99% ester, and between 99% and about 100% ester.

Compositions in accordance with the invention also include compositionscomprising 1,3-propanediol and an extract. The 1,3-propanediol of thesecompositions has at least 95% biobased carbon, or alternatively, the1,3-propanediol has 100% biobased carbon. The compositions comprising anextract and 1,3-propanediol can be between about 0.1% and about 5%1,3-propanediol, between about 0.5% and about 25% 1,3-propanediol,between about 25% and about 50% 1,3-propanediol, between about 50% andabout 75% 1,3-propanediol, and between about 75% and about 99%1,3-propanediol.

Compositions in accordance with the invention also include compositionscomprising both 1,3-propanediol and a conjugate ester of 1,3-propanediolalong with an extract. The 1,3-propanediol of these compositions has atleast 95% biobased carbon, or alternatively, the 1,3-propanediol has100% biobased carbon. The compositions comprising an extract and amixture of 1,3-propanediol and a conjugate ester of 1,3-propanediol canbe between about 0.1% and about 5% mixture, between about 0.5% and about25% mixture, between about 25% and about 50% mixture, between about 50%and about 75% mixture, and between about 75% and about 99% mixture.

A mixture of a glycol and ester can be very effective in extractions,and the mixture can remove more active ingredients than either solventalone. More actives are extracted from plant material using a solventmixture because the esters (especially diesters) are non-polar, whereasglycol components are polar. Accordingly, the lipophilic ingredients caneasily be removed from the plants using the ester glycol mixture. Insome cases the density of an ester can be much higher than the densityof the glycol, and after the maceration process the “cake” (the extractof the ester) can easily solidify and separate from the glycol phase.Additionally, the esters can be volatile compounds and in extractionsthe esters can be easily evaporated to obtain concrete, fragrance oil,absolute, or enfleurage.

The 1,3-propanediol, the conjugate esters of 1,3-propanediol, andmixtures thereof can be effective as solvents and diluents when combinedwith other appropriate solvents, including water.

Biologically-Derived 1,3-propanediol

The present invention relates to compositions comprising a botanical,vegetal, protein/peptide, marine, algae, or milk extract or fragranceconcentrate or oil wherein biologically-derived 1,3-propanediol or itsester conjugate is employed as a chemical solvent for extraction ordiluent of the botantical, vegetal, protein/peptide, marine, algae, ormilk extract or fragrance concentrate or oil. “Biologically-derived”means that the 1,3-propanediol is synthesized by one or more species orstrains of living organisms, including particularly strains of bacteria,yeast, fungus and other microbes. Biologically-derived 1,3-propanedioluseful in shampoo or body wash compositions disclosed herein.

Biologically-derived 1,3-propanediol is collected in a high purity form.Such 1,3-propanediol has at least one of the followingcharacteristics: 1) an ultraviolet absorption at 220 nm of less thanabout 0.200 and at 250 nm of less than about 0.075 and at 275 nm of lessthan about 0.075; or 2) a composition having L*a*b* “b*” color value ofless than about 0.15 and an absorbance at 270 nm of less than about0.075; or 3) a peroxide composition of less than about 10 ppm; or 4) aconcentration of total organic impurities of less than about 400 ppm. A“b*” value is the spectrophotometrically determined Yellow Bluemeasurement as defined by the CIE L*a*b* measurement ASTM D6290.

The level of 1,3-propanediol purity can be characterized in a number ofdifferent ways. For example, measuring the remaining levels ofcontaminating organic impurities is one useful measure.Biologically-derived 1,3-propanediol can have a purity level of lessthan about 400 ppm total organic contaminants; preferably less thanabout 300 ppm; and most preferably less than about 150 ppm. The term ppmtotal organic purity refers to parts per million levels ofcarbon-containing compounds (other than 1,3-propanediol) as measured bygas chromatography.

Biologically-derived 1,3-propanediol can also be characterized using anumber of other parameters, such as ultraviolet light absorbance atvarying wavelengths. The wavelengths 220 nm, 240 nm and 270 nm have beenfound to be useful in determining purity levels of the composition.Biologically-derived 1,3-propaediol can have a purity level wherein theUV absorption at 220 nm is less than about 0.200 and at 240 nm is lessthan about 0.075 and at 270 nm is less than about 0.075.

Biologically-derived 1,3-propanediol can have a b* color value (CIEL*a*b*) of less than about 0.15.

The purity of biologically-derived 1,3-propanediol compositions can alsobe assessed in a meaningful way by measuring levels of peroxide.Biologically-derived 1,3-propanediol can have a concentration ofperoxide of less than about 10 ppm.

It is believed that the aforementioned purity level parameters forbiologically-derived and purified 1,3-propanediol (using methods similaror comparable to those disclosed in U.S. Patent Application No.2005/0069997) distinguishes such compositions from 1,3-propanediolcompositions prepared from chemically purified 1,3-propanediol derivedfrom petroleum sources.

1,3-propanediol produced biologically via fermentation is known,including in U.S. Pat. No. 5,686,276, U.S. Pat. No. 6,358,716, and U.S.Pat. No. 6,136,576, which disclose a process using arecombinantly-engineered bacteria that is able to synthesize1,3-propanediol during fermentation using inexpensive green carbonsources such as glucose or other sugars from plants. These patents arespecifically incorporated herein by reference. Biologically-derived1,3-propanediol can be obtained based upon use of the fermentation brothgenerated by a genetically-engineered Eschericia coli (E. coli), asdisclosed in U.S. Pat. No. 5,686,276. Other single organisms, orcombinations of organisms, may also be used to biologically produce1,3-propanediol, using organisms that have been genetically-engineeredaccording to methods known in the art. “Fermentation” refers to a systemthat catalyzes a reaction between substrate(s) and other nutrients toproduct(s) through use of a biocatalyst. The biocatalysts can be a wholeorganism, an isolated enzyme, or any combination or component thereofthat is enzymatically active. Fermentation systems useful for producingand purifying biologically-derived 1,3-propanediol are disclosed in, forexample, Published U.S. Patent Application No. 2005/0069997 incorporatedherein by reference.

The transformed E. coli DH5α containing cosmid pKP1 containing a portionof the Klebsiella genome encoding the glycerol dehydratase enzyme wasdeposited on 18 Apr. 1995 with the ATCC under the terms of the BudapestTreaty and is identified by the ATCC number ATCC 69789. The transformedE. coli DH5α containing cosmid pKP4 containing a portion of theKlebsiella genome encoding a diol dehydratase enzyme was deposited on 18Apr. 1995 with the ATCC under the terms of the Budapest Treaty and isidentified by the ATCC number ATCC 69790. As used herein, “ATCC” refersto the American Type Culture Collection international depository locatedat 10801 University Boulevard, Manassas, Va., 20110 2209, U.S.A. The“ATCC No.” is the accession number to cultures on deposit with the ATCC.

The biologically derived 1,3-propanediol (bio-PDO) for use in thecurrent invention, produced by the process described herein, containscarbon from the atmosphere incorporated by plants, which compose thefeedstock for the production of bio-PDO. In this way, the bio-PDOcontains only renewable carbon, and not fossil fuel based, or petroleumbased carbon. Therefore the use of bio-PDO and its conjugate esters hasless impact on the environment as the propanediol does not depletediminishing fossil fuels. The use of the use of bio-PDO and itsconjugate esters also does not make a net addition of carbon dioxide tothe atmosphere, and thus does not contribute to greenhouse gasemissions. Thus, the present invention can be characterized as morenatural and having less environmental impact than similar compositionscomprising petroleum based glycols.

Moreover, as the purity of the bio-PDO utilized in the compositions ofthe invention is higher than chemically synthesized PDO and otherglycols, risk of introducing impurities that may cause irritation isreduced by its use over commonly used glycols, such as propylene glycol.

In one embodiment of the invention, a composition comprising1,3-propanediol and an extraction product is provided, where the1,3-propanediol is biologically derived. The biologically-derived1,3-propanediol can have at least 85% biobased carbon, at least 95%biobased carbon, or 100% biobased carbon, when assessed by theapplication of ASTM-D6866 as described above.

A sample of biologically-derived 1,3-propanediol was analysized usingASTM method D 6866-05. The results received from Iowa State Universitydemonstrated that the above sample was 100% bio-based content. In aseparate analysis, also performed using a ASTM-D6866 method, chemical,or petroleum-based 1,3-propanediol (purchased from SHELL) was found tohave 0% bio-based content. Propylene glycol (USP grade from ALDRICH) wasfound to have 0% bio-based content.

It is contemplated herein that other renewably-based orbiologically-derived glycols, such as ethylene glycol or 1,2 propyleneglycol, diethylene glycol, triethylene glycol among others, can be usedin the extractions or compositions of the present invention.

There may be certain instances wherein the extractions or extractcompositions of the invention may comprise a combination of abiologically-derived 1,3-propanediol and one or more nonbiologically-derived glycol components, such as, for example, chemicallysynthesized 1,3-propanediol. In such occasions, it may be difficult, ifnot impossible to determine which percentage of the glycol compositionis biologically-derived, other than by calculating the bio-based carboncontent of the glycol component. In this regard, in the extractionsolvents and extract compositions of the invention, the 1,3-propanediolused as a solvent, or used to form 1,3 propanediol esters, can compriseat least about 1% bio-based carbon content up to 100% bio-based carboncontent, and any percentage there between.

Ester Conjugates of Biologically Derived 1,3-Propanediol

Esters of biologically derived 1,3-propanediol, “bio-PDO” can besynthesized by contacting bio-PDO with an organic acid. The organic acidcan be from any origin, preferably either a biosource or synthesizedfrom a fossil source. Most preferably the organic acid is derived fromnatural sources or bio-derived having formula R₁R₂—COOH. Where in thesubstituent R₁ can be saturated or unsaturated, substituted orunsubstituted, aliphatic or aromatic, linear or branched hydrocarbonhaving chain length 1 to 40 or their salts or alkyl esters. Where in thesubstituent R₂ can be H or COOH. The hydrocarbon chain can also have oneor more functional groups such as alkene, amide, amine, carbonyl,carboxylic acid, halide, hydroxyl groups. Naturally occurring organicacids produced esters containing all biobased carbon. These naturallyoccurring organic acids, especially those produced by a biologicalorganism, are classified as bio-produced and the resulting ester ordiester could thereby also be classified as bio-produced. Naturallyoccurring sources of such fatty acids include coconut oil, variousanimal tallows, lanolin, fish oil, beeswax, palm oil, peanut oil, oliveoil, cottonseed oil, soybean oil, corn oil, rape seed oil. Conventionalfractionation and/or hydrolysis techniques can be used if necessary toobtain the fatty acids from such materials.

Appropriate carboxylic acids for producing esters ofbiologically-derived 1,3-propanediol generally include: (1) C1-C3 carboncontaining mono carboxylic acids, including formic acid and acetic acid;(2) fatty acids, such as those acids containing four or more carbonatoms; (3) saturated fatty acids, such as butyric acid, caproic acid,valeric acid, caprylic acid, capric acid, lauric acid, myristic acid,palmitic acid, stearic acid, arachidic acid, and behenic acid; (4)unsaturated fatty acids, such as oleic acid, linoleic acid, and euricicacid; (5) polyunsaturated fatty acids, such as alpha-linolenic acid,stearidonic acid (or moroctic acid), eicosatetraenoic acid, omega-6fatty acids, arachidonic acids, and omega-3 fatty acids,eicosapentaenoic acid (or timnodonic acid), dosocapentaenoic acid (orclupanodonic acid), and docosahexaenoic acid (or cervonic acid); (6)hydroxy fatty acids, such as 2-hydroxy linoleic acid, and recinoleicacid; phenylalkanoic fatty acids, such as 11-phenyl undecanoic acid,13-phenyl tridecanoid acid, and 15-phenyl tridecanoid acid; and (7)cyclohexyl fatty acids, such as 11-cyclohexyl undecanoic acid, and13-cyclohexyl tridecanoic acid.

The following acids and their salts or alkyl esters are specificallyuseful, acetic, butyric, lauric, myristic, palmitic, stearic, arachidic,adipic, benzoic, caprylic, maleic, palmitic, sebacic, archidonic,erucic, palmitoleic, pentadecanoic, heptadecanoic, nondecanoic,octadectetraenoic, eicosatetraenoic, eicosapentaenoic, docasapentaenoic,tetracosapentaenoic, tetrahexaenoic, docosahexenoic, (alpha)-linolenic,docosahexaenoic, eicosapentaenoic, linoleic, arachidonic, oleic, erucic,formic, prop ionic, valeric, caproic, capric, malonic, succinic,glutaric, adipic, pimelic, suberic, azelaic, tartaric, citri c,salicylic, acetyl-salicylic, pelargonic, behenic, cerotic, margaric,montanic, melissic, lacceroic, ceromelissic, geddic, ceroplasticundecylenic, ricinoleic, and elaeostearic acid as well as mixtures ofsuch acids. A more preferred list of suitable organic acids are acetic,adipic, benzoic, maleic, sebacic, and mixtures of such acids. A morepreferred list of suitable “fatty acids” meaning generally acids namedcontaining 8-40 carbon in the carbon useful in the present inventioninclude butyric, valeric, caproic, caprylic, pelargonic, capric, lauric,myristic, palmitic, stearic, arachidic, behenic, cerotic, oleic,linoleic, linolenic, margar ic, montanic, melissic, lacceroic,ceromelissic, geddic, ceroplastic and the mixtures of such acids. Amongthose acids, these acids, and their salts and alkyl esters are mostpreferred stearic, lauric, palmetic, oleic, 2-ethyl hexanoic, and12-hydroxystearic and mixtures of such acids.

The esters produced include all the appropriate conjugate mono anddiesters of 1,3 propanediol using the described organic acids. Someesters in particular that are produced include propanediol distearateand monostearate, propandiol dilaurate and monolaurate, propanedioldioleate and monooleate, propanediol divalerate and monovalerate,propanediol dicaprylate and monocaprylate, propanediol dimyristate andmonomyristate, propanediol dipalmitate and monopalmitate, propanedioldibehenate and monobehenate, propanediol adipate, propanediol maleate,propanediol dibenzoate, propanediol diacetate, and all mixtures thereof.

In particular, the esters produced include: propanediol distearate andmonostearate, propanediol dioleate and monooleate, propanedioldicaprylate and monocaprylate, propanediol dimyristate andmonomyristate, and all mixtures thereof.

Generally 1,3-propanediol can be contacted, preferably in the presenceof an inert gas reacted with a fatty acid or mixture of fatty acids orsalts of fatty acids in the absence or presence of a catalyst or mixtureof two or more catalysts, at temperatures ranging from 25° C. to 400° C.

During the contacting, water is formed and can be removed in the inertgas stream or under vacuum to drive the reaction complete. Any volatilebyproducts can be removed similarly. When the reaction is complete, theheating can be stopped and cooled.

The catalyst can be removed preferably by dissolving and removing indeionized water. If catalyst can be removed by treating with deionizedwater, the reaction mixture is treated with aqueous solutions of acid orbase to forms salts and removing the salts either by washing orfiltering.

Further purification to obtain high purity fatty esters, preferably forpharmaceutical application can be carried out by dissolving in a solventthat dissolves fatty ester easily at higher temperatures and least atlower temperatures and recrystallyzing with or without addition ofadditional solvent at low temperatures.

The catalyst can be an acid for non-limiting examples, sulfuric acid, orp-toluene sulfonic acid. The catalyst can also be a base, fornon-limiting example, sodium hydroxide. The catalyst can also be a salt,for non-limiting example, potassium acetate. The catalyst can also be analkoxide, for non-limiting example, titanium tetraisopropoxide. Thecatalyst can also be a heterogeneous catalyst, for non-limitingexamples: zeolite, heteropolyacid, amberlyst, or ion exchange resin. Thecatalyst can also be a metal salt, for non-limiting examples, tinchloride, or copper chloride, The catalyst can also be an enzyme, suchas those known in the art. The catalyst can also be an organic acid, fora non-limiting example, formic acid. Finally the catalyst can also be anorganometalic compound, for non-limiting example, n-butylstannoic acid.

This process can be carried out in the presence or absence of a solvent.If a solvent is not necessary to facilitate the production of fattyester, it is preferred that the process is carried out in the absence ofsolvent.

The process can be carried out at atmospheric pressure or under vacuumor under pressurized conditions.

Where R₁ and R₂ is a hydrocarbon, preferably with a carbon chain lengthof about 1 to about 40. Such hydrocarbons can be saturated orunsaturated, substituted or unsubstituted, linear or branched

M is hydrogen, an alkali metal or an alkyl group.

Where R₁ is a hydrocarbon, preferably with a carbon chain length ofabout 1 to about 40. Such hydrocarbons can be saturated or unsaturated,substituted or unsubstituted, linear or branched. M is hydrogen, analkali metal or an alkyl group.

Compositions in accordance with the invention comprise esters in whichR1 has one or more functional groups selected from the group consistingof alkene, amide, amine, carbonyl, carboxylic acid, halide, hydroxylgroups, ether, alkyl ether, sulfate and ethersulfate. The esters canhave the formula R1-C(═O)—O—CH2-CH2-CH2-O—C(═O)—R2, wherein both R1 andR2 are linear or branched carbon chains of a length between about 1 anabout 40 carbons. R1 and R2 can have one or more functional groupsselected from the group consisting of alkene, amide, amine, carbonyl,carboxylic acid, halide, hydroxyl groups, ether, alkyl ether, sulfateand ethersulfate. Additionally, R1 and R2 can be the same carbon chainin the case of a diester.

Any molar ratio of diol to dicarboxylic acid or its salt or its estercan be used. The preferred range of the diol to dicarboxylic acid isfrom about 1:3 to about 2:1. This ratio can be adjusted to shift thefavor of the reaction from monoester production to diester production.Generally, to favor the production of diesters slightly more than abouta 1:2 ratio is used; whereas to favor the production of monoesters abouta 1:1 ratio is used. In general, if the diester product is desired overthe monoester the ratio of diol to dicarboxylic acid can range fromabout 1.01:2 to about 1.1:2; however if the monoester is desired a rangeof ratios from about 1.01:1 to about 2:1 is used.

The catalyst content for the reaction can be from 1 ppm to 60 wt % ofthe reaction mixture, preferably from 10 ppm to 10 wt %, more preferablyfrom 50 ppm to 2 wt % of the reaction mixture.

The product may contain diesters, monoesters or combination diesters andmonoesters and small percentage of unreacted acid and diol depending onthe reaction conditions. Unreacted diol can be removed by washing withdeionized water. Unreacted acid can be removed by washing with deionizedwater or aqueous solutions having base or during recrystallization.

Any ester of 1,3-propanediol can be made or used in accordance with thepresent invention. Short, middle and long chain monoesters and diestersof the 1,3-propanediol can be made. Specifically those acids containingbetween about 1 and about 36 carbons in the alkyl chain can be produced.More specifically, the following monoesters and diesters can beproduced: propanediol distearate (monostearate and the mixture),propandiol dilaurate (monolaurate and the mixture), propanediol dioleate(monooleate and the mixture), propanediol divalerate (monovalerate andthe mixture), propanediol dicaprylate (monocaprylate and the mixture),propanediol dimyristate (monomyristate and the mixture), propanedioldipalmitate (monopalmitate and the mixture), propanediol dibehenate(monobehenate and the mixture), propanediol adipate, propanediolmaleate, propanediol dibenzoate, and propanediol diacetate.

For compositions comprising an extract and 1,3-propanediol, theconjugate esters of 1,3-propanediol, or mixtures thereof, the extractcan be a compound or group of compounds that are extracted from a sourcematerial. In some applications, the extract is extracted from a naturalsource, such as a botanical source. Examples of appropriate naturalextracts include botanical extracts, vegetal extracts, protein extracts,lipid extracts, marine extracts, algae extracts, and milk extracts.

Botanical sources for extracts include the following list of families ofplants and trees: Acanthaceae, Aceraceae, Achariaceae, Achatocarpaceae,Acoraceae, Actinidiaceae, Actiniopteridaceae, Adiantaceae, Adoxaceae,Aegicerataceae, Aetoxicaceae, Agavaceae, Agdestidaceae, Aitoniaceae,Aizoaceae, Akaniaceae, Alangiaceae, Alismataceae, Alliaceae,Alseuosmiaceae, Alstroemeriaceae, Altingiaceae, Alzateaceae,Amaranthaceae, Amaryllidaceae, Amborellaceae, Ampelidaceae,Anacardiaceae, Anarthriaceae, Ancistrocladaceae, Androstachydaceae,Anemiaceae, Angiopteridaceae, Anisophylleaceae, Annonaceae,Anthericaceae, Antoniaceae, Aphyllanthaceae, Apiaceae, Apocynaceae,Aponogetonaceae, Apostasiaceae, Aquifoliaceae, Araceae, Araliaceae,Araucariaceae, Arecaceae, Aristolochiaceae, Asclepiadaceae,Asparagaceae, Asphodelaceae, Aspidiaceae, Aspleniaceae, Asteliaceae,Asteraceae, Asteranthaceae, Asteranthaceae, Asteranthaceae,Asteranthaceae, Aucubaceae, Austrobaileyaceae, Avicenniaceae,Azollaceae, Balanopaceae, Balanophoraceae, Balsaminaceae, Bambuseae,Barringtoniaceae, Basellaceae, Bataceae, Begoniaceae, Berberidaceae,Betulaceae, Bignoniaceae, Bischofiaceae, Bixaceae, Blechnaceae,Bombacaceae, Bonnetiaceae, Boraginaceae, Botrychiaceae, Brassicaceae,Bruniaceae, Brunoniaceae, Buddlejaceae, Burmanniaceae, Burseraceae,Butomaceae, Buxaceae, Byblidaceae, Byttneriaceae, Cabombaceae,Cactaceae, Caesalpiniaceae, Callitrichaceae, Calycanthaceae,Calyceraceae, Campanulaceae, Canellaceae, Cannabidaceae, Cannaceae,Canotiaceae, Capparidaceae, Caprifoliaceae, Cardiopteridaceae,Caricaceae, Carlemanniaceae, Caryocaraceae, Caryophyllaceae,Casuarinaceae, Cayceraceae, Cecropiaceae, Celastraceae,Centrolepidaceae, Cephalotaceae, Cephalotaxaceae, Ceratophyllaceae,Cercidiphyllaceae, Chemopleuriaceae, Chenopodiaceae, Chloanthaceae,Chloranthaceae, Christenseniaceae, Chrysobalanaceae, Cistaceae,Clethraceae, Clusiaceae, Cneoraceae, Cochlospermaceae, Columelliaceae,Combretaceae, Commelinaceae, Compositae, Connaraceae, Conocephalaceae,Convolvulaceae, Coriariaceae, Cornaceae, Corynocarpaceae, Costaceae,Crassulaceae, Crossosomataceae, Crypteroniaceae, Cryptogrammaceae,Cucurbitaceae, Culcitaceae, Cunoniaceae, Cupressaceae, Cyanastraceae,Cyatheaceae, Cycadaceae, Cyclanthaceae, Cyclocheilaceae, Cymodoceaceae,Cynomoriaceae, Cyperaceae, Cypripediaceae, Cyrillaceae, Danaeaceae,Daphniphyllaceae, Datiscaceae, Davalliaceae, Davidsoniaceae,Degeneriaceae, Dennstaedtiaceae, Dialypetalanthaceae, Diapensiaceae,Dichapetalaceae, Dicksoniaceae, Dicrastylidaceae, Didiereaceae,Didymelaceae, Diegodendraceae, Dilleniaceae, Dioscoreaceae, Dipsacaceae,Dipteridaceae, Dipterocarpaceae, Dracaenaceae, Droseraceae,Dryopteridaceae, Dysphaniaceae, Dysphaniaceae, Ebenaceae,Ecdeiocoleaceae, Elaeagnaceae, Elaeocarpaceae, Elaphoglossaceae,Elatinaceae, Empetraceae, Epacridaceae, Ephedraceae, Equisetaceae,Ericaceae, Eriocaulaceae, Erythropalaceae, Erythroxylaceae,Escalloniaceae, Eucommiaceae, Eucryphiaceae, Euphorbiaceae,Eupomatiaceae, Eupteleaceae, Fabaceae, Fagaceae, Flacourtiaceae,Flagellariaceae, Fouquieriaceae, Frankeniaceae, Fumariaceae, Garryaceae,Geissolomataceae, Gentianaceae, Geosiridaceae, Geraniaceae,Gesneriaceae, Ginkgoaceae, Gleicheniaceae, Globulariaceae, Gnetaceae,Goetzeaceae, Gomortegaceae, Goodeniaceae, Goupiaceae, Gramineae,Grammitaceae, Grammitidaceae, Grubbiaceae, Gunneraceae, Guttiferae,Gyrostemonaceae, Haemodoraceae, Haloragaceae, Haloragidaceae,Hamamelidaceae, Heliconiaceae, Helminthostachyaceae, Hemionitidaceae,Hernandiaceae, Heteropyxidaceae, Himantandraceae, Hippocastanaceae,Hippocrateaceae, Hippuridaceae, Hoplestigmataceae, Hostaceae,Humiriaceae, Hydnoraceae, Hydrangeaceae, Hydrocharitaceae,Hydrocotylaceae, Hydrophyllaceae, Hydrostachyaceae, Hymenophyllaceae,Hymenophyllopsidaceae, Hypericaceae, Hypolepidaceae, Hypoxidaceae,Icacinaceae, Idiospermaceae, Illiciaceae, Iridaceae, Isoetaceae,Ixonanthaceae, Juglandaceae, Julianiaceae, Juncaceae, Juncaginaceae,Koeberliniaceae, Krameriaceae, Labiatae, Lacistemataceae, Lactoridaceae,Lamiaceae, Lardizabalaceae, Lauraceae, Lecythidaceae, Leeaceae,Leguminosae, Leitneriaceae, Lemnaceae, Lennoaceae, Lentibulariaceae,Lilaeaceae, Liliaceae, Limnanthaceae, Limnocharitaceae, Linaceae,Lindsaeaceae, Lissocarpaceae, Loasaceae, Lobeliaceae, Loganiaceae,Lomariopsidaceae, Lophosoriaceae, Loranthaceae, Lowiaceae,Loxogrammaceae, Loxsomaceae, Lunulariaceae, Luzuriagaceae,Lycopodiaceae, Lygodiaceae, Lythraceae, Magnoliaceae, Malesherbiaceae,Malpighiaceae, Malvaceae, Marantaceae, Marattiaceae, Marcgraviaceae,Marchantiaceae, Marsileaceae, Martyniaceae, Matoniaceae, Mayacaceae,Medusagynaceae, Medusandraceae, Melastomataceae, Meliaceae,Melianthaceae, Menispermaceae, Menyanthaceae, Metaxyaceae, Mimosaceae,Misodendraceae, Monimiaceae, Moraceae, Moraceae, Moringaceae, Musaceae,Myoporaceae, Myricaceae, Myristicaceae, Myrothamnaceae, Myrsinaceae,Myrtaceae, Najadaceae, Negripteridaceae, Nelumbonaceae, Nepenthaceae,Nephrolepidaceae, Nolanaceae, Nyctaginaceae, Nymphaeaceae, Nyssaceae,Ochnaceae, Octoknemaceae, Olacaceae, Oleaceae, Oleandraceae, Oliniaceae,Onagraceae, Oncothecaceae, Onocleaceae, Ophioglossaceae, Opiliaceae,Orchidaceae, Orobanchaceae, Osmundaceae, Oxalidaceae, Paeoniaceae,Pandaceae, Pandanaceae, Papaveraceae, Parkeriaceae, Passifloraceae,Pedaliaceae, Penaeaceae, Pentaphragmataceae, Pentaphylacaceae,Peperomiaceae, Peraceae, Peranemaceae, Periplocaceae, Petrosaviaceae,Philesiaceae, Philydraceae, Phormiaceae, Phrymaceae, Phytolaccaceae,Pinaceae, Piperaceae, Pittosporaceae, Plagiogyriaceae, Plantaginaceae,Platanaceae, Platyzomataceae, Plumbaginaceae, Poaceae, Podocarpaceae,Podophyllaceae, Podostemaceae, Polemoniaceae, Polygalaceae,Polygonaceae, Polypodiaceae, Pontederiaceae, Portulacaceae, Potaliaceae,Potamogetonaceae, Primulaceae, Proteaceae, Psilotaceae, Pteridaceae,Punicaceae, Pyrolaceae, Quiinaceae, Rafflesiaceae, Ranunculaceae,Rapateaceae, Rebouliaceae, Resedaceae, Restionaceae, Rhamnaceae,Rhizophoraceae, Rhoipteleaceae, Rhoipteleaceae, Rhopalocarpaceae,Roridulaceae, Rosaceae, Rubiaceae, Ruscaceae, Rutaceae, Sabiaceae,Saccifoliaceae, Salicaceae, Salvadoraceae, Salviniaceae, Santalaceae,Sapindaceae, Sapotaceae, Sarcolaenaceae, Sarcospermataceae,Sarraceniaceae, Saururaceae, Saxifragaceae, Scheuchzeriaceae,Schisandraceae, Schizaeaceae, Scrophulariaceae, Scyphostegiaceae,Scytopetalaceae, Selaginaceae, Selaginellaceae, Simaroubaceae,Sinopteridaceae, Smilacaceae, Solanaceae, Sonneratiaceae, Sparganiaceae,Sphaerosepalaceae, Sphenostemonaceae, Stachyuraceae, Stackhousiaceae,Staphyleaceae, Stemonaceae, Sterculiaceae, Strasburgeriaceae,Strelitziaceae, Stromatopteridaceae, Strychnaceae, Styracaceae,Symplocaceae, Taccaceae, Taenitidaceae, Tamaricaceae, Taxaceae,Taxodiaceae, Tecophilaeaceae, Tepuianthaceae, Tetracentraceae,Tetragoniaceae, Tetrameristaceae, Theaceae, Theligonaceae,Thelypteridaceae, Theophrastaceae, Thunbergiaceae, Thurniaceae,Thymelaeaceae, Thyrsopteridaceae, Tichodendraceae, Tiliaceae,Tmesipteridaceae, Tovariaceae, Trapaceae, Tremandraceae, Trigoniaceae,Trilliaceae, Triuridaceae, Trochodendraceae, Tropaeolaceae, Turneraceae,Typhaceae, Uapacaceae, Ulmaceae, Urticaceae, Vacciniaceae, Vahliaceae,Valerianaceae, Velloziaceae, Verbenaceae, Violaceae, Vitaceae,Vittariaceae, Vivianiaceae, Vochysiaceae, Welwitschiaceae, Winteraceae,Xanthorrhoeaceae, Xyridaceae, Zamiaceae, Zingiberaceae, Zosteraceae,Zygophyllaceae.

Preferred families of plants and trees include Anacardiaceae Araceae,Balanopaceae, Balsaminaceae, Begoniaceae, Boraginaceae, Buxaceae,Caricaceae, Cucurbitaceae, Clusiaceae, Daphniphyllaceae, Ericaceae,Euphorbiaceae, Fabaceae, Fagaceae, Hippocastanaceae, Hostaceae,Hydrangeaceae, Labiateae, Lilaeaceae, Magnoliaceae, Moringaceae,Myristicaceae, Myrtaceae, Oleaceae, Orchidaceae, Peperomiaceae,Pinaceae, Primulaceae, and Rutaceae.

The preferred species of plants and trees for extract sources includeAchillea millefolium, Aesculus chinensis, Allium sativum, Artemisiaapiacea, Astrocaryum murumuru, Bactris gasipaes, Benincasa hispida,Celastrus paniculatus, Cetraria islandica, Chenopodium quinoa, Cinchonasuccirubra, Citrus bergamia, Citrus sinensis, Coriandrum sativum, Codiumtomentosum, Commiphora molmol, Crataegus cuneata, Cucumis sativus,Eucalyptus globulus, Gleditsia sinensis, Gnetum amazonicum, Hibiscusrosa-sinensis, Jasminum officinale, Lonicera caprifolium, Lonicerajaponica, Lycopersicon esculentum, Malus pumila, Matricaria recutita,Maximiliana maripa, Melaleuca hypericifolia, Melaphis chinensis, Menthapiperita, Mouriri apiranga, Nasturtium officinale, Nelumbo nucifera,Oenothera biennis, Ophiopogon japonicus, Persea americana, Paffiapaniculata, Phellodendron amurense, Phyllanthus emblica, Pisum sativum,Potentilla erecta, Pterocarpus santalinus, Rehmannia chinensis, Resedaluteola, Ribes nigrum, Rosa centifolia, Rubus thunbergii, Spondiasamara, Styrax benzoin, and Thymus vulgaris.

Extract sources also include algae. Families of algae used as extractsources include Acrochaeticaceae, Characeae, Codiaceae, Fucaceae,Laminariaceae, Lemaneaceae, Ulvaceae, and Pamariaceae. Preferred algaespecies include Lemanea fluviatilis (red algea), (L.), Ascophyllumnodosum (brown alga), Lemanea fluviatilis, Lemanea fucina (red algea),Ulva lactuca (green alga), Laminaria digitata, Laminaria ochroleuca.

Extract sources also include members of the kingdom of Fungi. Forextraction classes of Homobasidiomycetes (or true mushrooms) can beused. Some exemplary mushrooms families include: Meripilaceae,Tricholomataceae, and Ganodermataceae (maitake, shiitake, reishimushrooms). Specific species include: Agaricus bisporus, Agaricuscampestris, Flammulina velutipes Hypsizygus tessulatus, Lentinus edodes,Phellinus linteus, Pleurotus cornucopiae, Pleurotus ostreatus, Tremellafuciformis, Sparassis crispa, Tuber magnatum, and Volvariella volvacea.

Species from the division of Bryophyta, Kingdom of plantae (whichincludes mosses) can be used as extract sources, and some species oflichen can also be used for extraction.

Marine sources, such as plants, algae, plankton, and fish, are used toproduce extracts. Protein and lipid extract sources include plant,animal, fish and human (eg. Placenta) materials. Milk can be used as anextract source to isolate and concentrate proteins, peptides, andlipids.

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While the compositions and methods of the present disclosurehave been described in terms of preferred embodiments, it will beapparent to those of skill in the art that variations may be applied tothe compositions and methods and in the steps or in the sequence ofsteps of the method described herein without departing from the concept,spirit, and scope of the invention. More specifically, it will beapparent that certain agents which are chemically related may besubstituted for the agents described herein while the same or similarresults would be achieved. All such similar substitutes andmodifications apparent to those skilled in the art are deemed to bewithin the spirit, scope, and concept of the invention as defined by theappended claims.

Personal Care Compositions

The personal care compositions of the present invention include anycomposition that may be applied to the skin, hair, eyelashes, eyebrows,lips, or nails to provide a cosmetic or beneficial effect. Thesepersonal care compositions include, but are not limited to, skin carecompositions, skin cleansing compositions, make-up, facial lotions,cream moisturizers, body washes, body lotions, foot creams, hand creams,lipstick, eyeshadow, foundation, facial powders, deodorant, shavingcream compositions, nail polishes, shaving lotions, cream depilatories,lotion depilatories, facial masks made with clay materials, anti-agingproducts, shampoos, hair conditioners, hair treatment creams, stylinggels, styling foams, hair mousses, hair sprays, set lotions,blow-styling lotions, hair color lotions, and hair relaxingcompositions.

In cosmetic compositions, biologically-derived 1,3-propanediol ispresent in amounts up to about 50% by weight based on the weight of thetotal composition, preferable up to about 35% by weight, and morepreferable up to about 10% by weight of the total composition.

In other personal care compositions, biologically-derived1,3-propanediol is present in amounts up to about 12% by weight based onthe weight of the total composition, though some compositions, forexample hair gels and deodorants, can contain up to about 30% by weightor 40% by weight, respectively, biologically-derived 1,3-propanediolbased on the weight of the total composition.

The personal care compositions of the present invention also may one ormore conventional cosmetic or dermatological additives or adjuvants,including, but not limited to, fillers, surfactants, thixotropic agents,antioxidants, preserving agents, dyes, pigments, fragrances, thickeners,vitamins, hormones, moisturizers, UV absorbing organic sunscreens, UVscattering inorganic sunscreens, wetting agents, cationic, anionic,nonionic or amphoteric polymers, and hair coloring active substances.These adjuvants are well known in the field of cosmetics and aredescribed in many publications, for example see Harry's Cosmeticology,8th edition, Martin Rieger, ed., Chemical Publishing, New York (2000).

Among these adjuvants, the fillers are generally present in personalcare products in a maximum proportion of about 99.9% by weight relativeto the total weight of the composition. These fillers, in the form ofvery fine powders, can be of natural or synthetic origin and include,but are not limited to, mineral powders, such as talc, kaolin, mica,silica, silicates, alumina, zeolites, hydroxyapatite, sericite, titaniumdioxide, titanium micas, barium sulfate, calcium carbonate, calciumsulfate, bismuth oxychloride, boron nitride and metal powders such asaluminum powder; plant powder, such as corn starch, wheat starch or ricestarch powders; organic powders, such as polyamide powder, polyesterpowder, polytetrafluoroethylene powder, the powder of fluorinatedalkanes, polyethylene powder and other inert plastics. These variouspowders can also be coated, for example with metal salts of fatty acids,amino acids, lecithin, collagen, silicone corn pounds, fluoro compoundsor with any common coating agent.

The personal care compositions of this invention may also containsurfactants or wetting agents, preferably at about 0.001 to about 18%,more preferably at about 0.005 to about 15% by weight of the totalcomposition. The terms “surfactants” and “wetting agents” as used hereinrefer to surface-active agents which, when added to water, cause it topenetrate more easily into, or spread on the surface of anothermaterial, by reducing the surface tension of the water at the water-airor water-oil interface. By “surface active agent” is meant any compoundthat reduces surface tension when dissolved in water or water solutions.The selection of a surfactant for this purpose presents a wide range ofpossibilities known in the art. Suitable surfactants include, but arenot limited to, the following:

(1) anionic surfactants, such as metallic or alkanolamine salts of fattyacids for example sodium laurate and triethanolamine oleate; alkylbenzene sulfones, for example triethanolamine dodecyl benzene sulfonate;alkyl sulfates, for example sodium lauryl sulfate; alkyl ether sulfates,for example sodium lauryl ether sulfate (2 to 8 EO); sulfosuccinates,for example sodium dioctyl sulfonsuccinate; monoglyceride sulfates, forexample sodium glyceryl monostearate monosulfate; isothionates, forexample sodium isothionate; methyl taurides, for example Igepon T;acylsarcosinates, for example sodium myristyl sarcosinate; acylpeptides, for example Maypons and lamepons; acyl lactylates,polyalkoxylated ether glycollates, for example trideceth-7 carboxylicacid; phosphates, for example sodium dilauryl phosphate.

(2) cationic surfactants, such as amine salts, for example sapaminhydrochloride; quatenary ammonium salts, for example Quaternium 5,Quaternium 31 and Quaternium 18;

(3) amphoteric surfactants, such as imidazol compounds, for exampleMiranol; N-alkyl amino acids, such as sodium cocaminopropionate andasparagine derivatives; betaines, for example cocamidopropylebetaine;

(4) nonionic surfactants, such as fatty acid alkanolamides, for exampleoleic ethanolamide; esters or polyalcohols, for example Span;polyglycerol esters, for example that esterified with C12-18 fatty acidsand one or several OH groups; polyalkoxylated derivatives, for examplepolyoxy:polyoxyethylene stearate (available for example from McIntyreCo.); ethers, for example polyoxyethe lauryl ether (available forexample from Stepan Co., Northfield, Ill., as Stepanol® ES); esterethers, for example Tween®; amine oxides, for example coconut anddodecyl dimethyl amine oxides. Mixtures of two or more of the abovesurfactants can be employed in the compositions according to theinvention.

The personal care compositions of this invention may also containthixotropic or gelling agents, preferably at about 0.02 to about 20%,more preferably at about 0.05 to about 18% by weight of the totalcomposition. Suitable thixotropic or gelling agents include, but are notlimited to, stearates of aluminum, calcium, magnesium, potassium,sodium, or zinc; hydroxystearate, isostearate, laurate, linoleate,myristate, oleate, olivate, palmate, palmitate, tallowate, rosinate, andthe like, and fatty acid esters of glycol, triglycerides, mixtures offatty alcohols, cholesterol derivatives and in particularhydroxycholesterol, and clay minerals which swell in the presence ofoil, and in particular those belonging to the montmorillonite group.

The personal care compositions of this invention may also containantioxidants, preferably at about 0.001 to about 10%, more preferably atabout 0.01 to about 8% by weight of the total composition. Suitableantioxidants are ingredients, which assist in preventing or retardingspoilage. Examples of antioxidants suitable for use in the compositionsof the invention include, but are not limited to, potassium sulfite,sodium bisulfite, sodium erythrobate, sodium metabisulfite, sodiumsulfite, propyl gallate, cysteine hydrochloride, butylatedhydroxytoluene, butylated hydroxyanisole, and the like.

The personal care compositions of this invention may also containpreserving agents, preferably at about 0.001 to about 8%, morepreferably at about 0.01 to about 5% by weight of the total composition.Suitable preserving agents include, but are not limited to, benzoicacid, benzyl alcohol, benzylhemiformal, benzylparaben,5-bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitropropane-1,3-diol, butylparaben, phenoxyethanol, methyl paraben, ethyl paraben, propyl paraben,diazolidinyl urea, calcium benzoate, calcium propionate, captan,chlorhexidine diacetate, chlorhexidine digluconate, chlorhexidinedihydrochloride, chloroacetamide, chlorobutanol, p-chloro-m-cresol,chlorophene, chlorothymol, chloroxylenol, m-cresol, o-cresol, DEDMHydantoin, DEDM Hydantoin dilaurate, dehydroacetic acid, diazolidinylurea, dibromopropamidine diisethionate, DMDM Hydantoin, Phenonip®,Kathon® and all of those disclosed on pages 570 to 571 of the Cosmetic,Toiletry and Fragrance Association (CTFA) Cosmetic Ingredient Handbook,Second Edition, 1992, which is herein incorporated by reference.

The personal care compositions of this invention may also contain dyes,preferably at about 0.1 to about 15%, by weight of the totalcomposition. Suitable dyes include, but are not limited to, eosinderivatives such as D&C Red No. 21 and halogenated fluoresceinderivatives such as D&C Red No. 27, D&C Red Orange No. 5 in combinationwith D&C Red No. 21 and D&C Orange No. 10.

The personal care compositions of this invention may also containpigments, preferably at about 0.1 to about 15% by weight of the totalcomposition. Suitable pigments may be inorganic or organic oralternatively metal lakes and include, but are not limited to, titaniumdioxide, zinc oxide, barium oxide, D&C Red No. 36 and D&C Orange No. 17,the calcium lakes of D&C Red Nos. 7, 11, 31 and 34, the barium lake ofD&C Red No. 12, the strontium lake D&C Red No. 13, the aluminum lakes ofFD&C Yellow No. 5, of FD&C Yellow No. 6, of D&C Red No. 27, of D&C RedNo. 21, and of FD&C Blue No. 1, iron oxides, manganese violet, chromiumoxide, ultramarine blue, and carbon black particles.

The personal care compositions of this invention may also containfragrances, preferably at about 0.01 to about 10%, by weight of thetotal composition. Numerous fragrances, both natural and synthetic, arewell known in the art. For example, Secondini (Handbook of Perfumes andFlavors, Chemical Publishing Co., Inc., New York, 1990), incorporatedherein by reference, describes many of the natural and syntheticfragrances used in cosmetics. Suitable natural fragrances include, butare not limited, to jasmines, narcissus, rose, violet, lavender, mint,spice, vanilla, anise, amber, orange, pine, lemon, wintergreen,rosemary, basil, and spruce. Suitable synthetic fragrances include, butare no limited to, acetaldehyde, C7 to C16 alcohols, benzyl acetate,butyric acid, citric acid, isobutyl phenyl acetate, linalyl butyrate,malic acid, menthol, phenyl ethyl cinnamate, phenyl propyl formate,tannic acid, terpineol, vanillin, amyl salicylate, benzaldehyde,diphenyl ketone, indole, and the like.

The personal care compositions of this invention may also containthickeners, preferably at about 0.001 to about 25%, more preferably atabout 0.1 to about 15%, by weight of the total composition. Suitablethickeners include, but are not limited to, starch; gums, such as gumarabic or xanthan gum; carbomer polymers, such as Carbopol® 941, 940,934 (available from Union Carbide Co., Midland, Mich.), and Ultrez 10;kaolin or other clays, ethylene glycol monostearate, carboxyvinylpolymer, acrylic copolymers, hydroxyethyl cellulose, and hydroxypropylcellulose.

The personal care compositions of this invention may also containvitamins and/or coenzymes, preferably at about 0.001 to about 10%, morepreferably at about 0.01% to about 8%, most preferably at about 0.05% toabout 5% by weight of the total composition. Suitable vitamins include,but are not limited to, ascorbic acid and derivatives thereof; the Bvitamins, such as thiamine, riboflavin, pyridoxin, and the like; vitaminA and derivatives thereof; vitamin E and derivatives thereof; vitamin Dand vitamin K; as well as coenzymes such as thiamine pyrophosphate,flavin adenine dinucleotide, folic acid, pyridoxal phosphate,tetrahydrofolic acid, and the like.

The personal care compositions of this invention may also containhormones, preferably at about 0.0001 to about 0.01% by weight of thetotal composition. Suitable hormones include, but are not limited to,estrogen, progesterone, pregnenolone, testosterone, estradiol,hydrocortisone, and cortisone.

The personal care compositions of this invention may also containmoisturizers, preferably at about 0.1 to about 30%, more preferably atabout 0.5 to about 25%, most preferably at about 1 to about 20% byweight of the total composition. These moisturizers includewater-soluble, low molecular weight moisturizers, fat-soluble, lowmolecular weight moisturizers, water-soluble, high molecular weightmoisturizers and fat-soluble, high molecular weight moisturizers.Suitable water-soluble, low molecular weight moisturizers include, butare not limited to, serine, glutamine, sorbitol, mannitol,pyrrolidone-sodium carboxylate, glycerin, propylene glycol, 1,3-butyleneglycol, ethylene glycol, polyethylene glycol (polymerization degree n=2or more), polypropylene glycol (polymerization degree n=2 or more),polyglycerin (polymerization degree n=2 or more), lactic acid andlactate. The water soluble, low molecular weight moisturizer can also bebiologically-derived 1,3-propanediol. Suitable fat-soluble, lowmolecular weight moisturizers include, but are not limited to,cholesterol and cholesterol ester. Suitable water-soluble, highmolecular weight moisturizers include, but are not limited to,carboxyvinyl polymers, polyaspartate, tragacanth, xanthane gum, methylcellulose, hydroxymethyl cellulose, hydroxyethyl cellulose,hydroxypropyl cellulose, carboxymethyl cellulose, water-soluble chitin,chitosan and dextrin. Suitable fat-soluble, high molecular weightmoisturizers include, but are not limited to,polyvinylpyrrolidone-eicosene copolymers,polyvinylpyrrolidone-hexadecene copolymers, nitrocellulose, dextrinfatty acid ester and high molecular silicone.

The personal care compositions of this invention may also contain UVabsorbing organic sunscreens, preferably at about 0.001 to about 20%,more preferably at about 0.01 to about 10%, most preferably at about0.05 to about 8% by weight of the total composition. UV absorbingorganic sunscreens are herein defined as organic chemicals that absorbultraviolet light of wavelengths between 290 and 329 nm. Suitable UVabsorbing organic sunscreens include, but are not limited to,para-aminobenzoic acid, ethyl para-aminobenzoate, amylpara-aminobenzoate, octyl para-aminobenzoate, ethylene glycolsalicylate, phenyl salicylate, octyl salicylate, benzyl salicylate,butylphenyl salicylate, homomethyl salicylate, benzyl cinnamate,2-ethoxyethyl para-methoxycinnamate (such as Parsol® available fromGivaudan-Roure Co.), octyl para-methoxycinnamate, glycerylmono(2-ethylhexanoate)dipara-methoxycinnamate, isopropylpara-methoxycinnamate, diisopropyl-diisopropylcinnamic acid estermixtures, urocanic acid, ethyl urocanate, hydroxymethoxybenzophenone,hydroxymethoxybenzophenonesulfonic acid and salts thereof,dihydroxymethoxybenzophenone, sodiumdihydroxymethoxybenzophenonedisulfonate, dihydroxybenzophenone,tetrahydroxybenzophenone, 4-tert-butyl-4′-methoxydibenzoylmethane,2,4,6-trianilino-p-(carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine, and2-(2-hydroxy-5-methylphenyl)benzotriazole. UV scattering inorganicsunscreen materials, such as inorganic pigments and metal oxides,including but not limited to oxides of titanium (such as SunSmartavailable from Cognis Corp), zinc, and iron, may also be incorporatedinto the compositions of the instant invention. UV scattering inorganicsunscreens are herein defined as inorganic substances that scatterultraviolet light of wavelengths between 210 and 280 nm. These UVscattering inorganic sunscreens may be used in the personal carecompositions of this invention at concentrations of preferably about0.001 to about 40%, more preferably at about 0.01 to about 10%, mostpreferably at about 0.05 to about 8% by weight of the total composition.

The personal care compositions of this invention may also contain otherfilm-forming polymers, preferably at about 0.01 to about 20%, morepreferably at about 0.01% to about 10%, by weight of the totalcomposition. These polymers serve as conditioners to coat the skin orhair, or to coat particles that are present in the composition. Thesepolymers may be cationic, anionic, nonionic, or amphoteric. Cationicpolymers are herein defined as synthetic or natural polymers thatcontain, or have been modified to contain, positively charged groupsand/or groups that can ionize to positively charged groups. Suitablecationic polymers, include, but are not limited to, cationizedcellulose, cationized guar gum, diallyly quaternary ammoniumsalt/acrylamide copolymers, quaternized polyvinylpyrrolidone andderivatives thereof, polyquaternium-1, polyquaternium-2,polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-8,polyquaternium-9, polyquaternium-11, polyquaternium-12,polyquaternium-13, polyquaternium-14, polyquaternium-15,polyquaternium-16, polyquaternium-17, polyquaternium-18,polyquaternium-19, polyquaternium-20, polyquaternium-22,polyquaternium-27, polyquaternium-28, polyquaternium-29,polyquaternium-30, and mixtures thereof, wherein the compounddesignation is the name adopted for the compound by the CTFA, and foundin the CTFA International Cosmetic Ingredient Dictionary, J. Nikitakis,ed., Cosmetic, Toiletry and Fragrance Association, Inc., Washington,D.C. (1991), incorporated herein by reference.

Anionic polymers are herein defined as synthetic or natural polymersthat contain, or have been modified to contain, negatively chargedgroups and/or groups that can ionize to negatively charged groups.Suitable anionic polymers, include, but are not limited to, polyacrylicacid, polymethacrylic acid, carboxymethylcellulose,hydroxymethylcellulose, and starch.

Nonionic polymers are herein defined as synthetic or natural polymersthat do not contain any charged groups. Suitable nonionic polymers,include, but are not limited to, polyvinylpyrrolidone, polyvinylalcohol, polyethylene glycol, polyvinylacetate, polysiloxanes, andcopolymers of vinylpyrrolidone and vinyl acetate.

Amphoteric polymers are herein defined as synthetic or natural polymersthat contain both negatively and positively charged groups and/or groupsthat can ionize to give positively and negatively charged groups.Suitable amphoteric polymers are described by Marchi et al. in U.S. Pat.No. 5,643,672, incorporated herein by reference. Examples include, butare not limited to, polymers resulting from the copolymerization of amonomer derived from a vinyl compound carrying a carboxyl group, such asacrylic acid, methacrylic acid, maleic acid and alpha-chloroacrylicacid, and a basic monomer derived from a substituted vinyl compoundcontaining at least one basic nitrogen atom, such asdialkylaminoalkyl(meth)acrylates and dialkylaminoalkyl(meth)acrylamides,products sold by the company National Starch under the name Amphomer®,methyl methacrylate/ethyldimethylcarboxymethylammonium methacrylatecopolymers, such as the products sold by Chimex under the name MexomerPX (CTFA name: “polyquaternium-30”),methacryloylethylbetaine/methacrylate copolymer sold by Sandoz under thename Diaformer, the methacryloylethylbetaine/methacrylate copolymer soldby Amerchol under the name Amersette, polysiloxane polyorganobetainecopolymers sold by Goldschmidt under the name Abil® B 9950 (CTFA Name:“Dimethicone PropylPG-Betaine”), the polydimethylsiloxane containingalkylphosphobetaine groups sold by Siltech under the name Pecosil®SPB-1240, and the oxyethyleneoxypropylene organobetaine/siloxanecopolymer sold by Goldschmidt under the name BC 1610.

According to one embodiment of the present invention, the compositionsare anhydrous and comprise a fatty phase in a proportion generally offrom about 10 to about 90% by weight relative to the total weight of thecomposition, wherein the fatty phase contains at least one liquid, solidor semi-solid fatty substance. The fatty substances include, but are notlimited to oils, fats, waxes, gums, and so-called pasty fattysubstances. The oils in the fatty phase may be of mineral, animal, plantor synthetic origin, and may or may not be volatile at room temperature.

Oils of mineral origin include, but are not limited to, liquid paraffinand liquid petroleum jelly. Oils of animal origin include, but are notlimited to, squalene and squalane. Oils of plant origin include, but arenot limited to, sweet aim and oil, beauty-leaf oil, palm oil, avocadooil, jojoba oil, sesame oil, olive oil, castor oil and cereal germ oilssuch as, for example, wheatgerm oil. Synthetic oils include, but are notlimited to:

(1) esters of the following formula: R1-COOR2 in which: R1 represents ahigher fatty acid residue containing from 7 to 20 carbon atoms, and R2represents a hydrocarbon-based radical containing from 3 to 30 carbonatoms. These esters, include, but are not limited to: purcellin oil,butyl myristate, isopropyl myristate, cetyl myristate, isopropylpalmitate, butyl stearate, hexadecyl stearate, isopropyl stearate, octylstearate, isocetyl stearate, decyl oleate, hexyl laurate, isononylisononanoate and esters derived from lanolic acid, such as isopropyllanolate and isocetyl lanolate. Other synthetic oils include, but arenot limited to, isododecane (available for example from Exxon-MobilChemical Co., Houston, Tex., under the trade name of Isopar®),isohexadecane, polyisobutenes and hydrogenated polyisobutene, as well asacetylglycerides, octanoates and decanoates of polyalcohols such asthose of glycol and of glycerol, ricinoleates of alcohols or ofpolyalcohols, such as cetyl ricinoleate, propylene glycol dicaprylateand diisopropyl adipate;

(2) fatty alcohols including, but not limited to, oleyl alcohol,linoleyl alcohol, linolenyl alcohol, isostearyl alcohol andoctyldodecanol;

(3) ethoxylated oils and fats, including but not limited to,triglycerides with a polyethylene glycol chain inserted, ethoxylatedmono- and di-glycerides, polyethoxylated lanolins, ethoxylated butterderivatives,

polyethylene glycol derivatives of glyceryl cocoate, glyceryl caproate,glyceryl caprylate, glyceryl tallowate, glyceryl palmate, glycerylstearate, glyceryl laurate, glyceryl oleate, glyceryl ricinoleate, andglyceryl fatty esters derived from triglycerides, such as palm oil,almond oil, and corn oil, glyceryl tallowate, glyceryl cocoate, andpolyethylene glycol based polyethoxylated fatty alcohols such as PEG 40hydrogenated castor oil (commercially available under the tradenameCremophor® from BASF), PEG 7 glyceryl cocoate and PEG 20 glyceryllaurate (commercially available from Henkel under the tradenames Cetiol®HE and Lamacit® GML 20 respectively), and polyethylene glycol ethers ofceteryl alcohol such as Ceteareth 25 (available from BASF under thetrade name Cremophor® A25).

(4) silicone oils including, but not limited to, optionallyfunctionalized linear polydiorganosiloxanes, cyclicpolydiorganosiloxanes and in particular cyclotetra- andcyclopenta-dimethicones and organopolysiloxanes such as alkyl, alkoxy orphenyl dimethicones, and in particular phenyltrimethicone (availablefrom Dow Corning, Midland, Mich., as Simethicone and DC 200 Fluids);

(5) fluoro oils including, but not limited to, fluoroalkanes andfluoropolyethers, partially fluorinated hydrocarbon-based oils, andfluoropolymers represented by the monomer unit: X1X2C═CX3F wherein X1,X2, and X3 are independently H or F.

The waxes in the fatty phase may be of mineral, fossil, animal, plant orsynthetic origin or alternatively can be hydrogenated oils or fattyesters, which are solid at 25° C. The mineral waxes, include, but arenot limited to, microcrystalline waxes, paraffin, petroleum jelly andceresine. The fossil waxes, include, but are not limited to, ozoceriteand montan wax. The waxes of animal origin, include, but are not limitedto beeswax, spermaceti, lanolin wax and derivatives obtained fromlanolin such as lanolin alcohols, hydrogenated lanolin, hydroxylatedlanolin, acetylated lanolin, lanolin fatty acids and acetylated lanolinalcohol. The waxes of plant origin, include, but are not limited to,candelilla wax, carnauba wax, Japan wax and cocoa butter. The syntheticwaxes, include, but are not limited to, ethylene homopolymers, seracite,shea butter, and copolymers of ethylene and of a monomer correspondingto the formula: CH2=CH—R3 in which: R3 represents an alkyl radicalcontaining from 1 to 30 carbon atoms or an aryl or aralkyl radical. Thealkyl radical of 1 to 30 carbon atoms is preferably a methyl, ethyl,propyl, isopropyl, butyl, decyl, dodecyl or octadecyl radical. Waxesobtained by Fisher-Tropsch synthesis and silicone waxes may also beused.

The hydrogenated oils, which are solid at 25° C., include, but are notlimited to, hydrogenated castor oil, hydrogenated palm oil, hydrogenatedtallow and hydrogenated coconut oil. The fatty esters, which are solidat 25° C., include, but are not limited to, propylene glycolmonomyristate and myristyl myristate. Waxes which can be used in thecompositions according to the invention include, but are not limited to,cetyl alcohol, stearyl alcohol, mono-, di- and triglycerides which aresolid at 25° C., stearic monoethanolamide, colophony and its derivativessuch as glycol abietate and glyceryl abietate, sucroglycerides andcalcium, magnesium, zinc and aluminum oleates, myristates, lanolates,stearates and dihydroxystearates.

The pasty-type fatty substances can be of mineral, animal, plant orsynthetic origin. The pasty fatty substances include, but are notlimited to, synthetic esters such as arachidyl propionate, polyvinyllaurate, polyethylene waxes and organopolysiloxanes such asalkyldimethicones, alkoxydimethicones or dimethicone esters.

These anhydrous compositions can be in various forms including, but notlimited to, an oily gel, solid products, such as compacted or castpowders, or alternatively sticks such as, for example lipsticks. Whenthe compositions according to the present invention are in the form ofan oily gel, they generally contain a thixotropic or gelling agent,examples of which are given supra. The thixotropic agents can be presentin various proportions depending on the desired texture of thecompositions. However, in most cases, they are present in a proportionof from about 1 to about 20% by weight relative to the total weight ofthe composition.

The anhydrous compositions of the present invention may be used inparticular as skin care, skin cleansing, or make-up products. When theyare present in the form of make-up products, they can be foundations,mascaras, eyeliners, lipsticks, eyeshadows or blushers. Thesecompositions are generally colored and contain dyes and/or pigments ascosmetic adjuvants, which are described supra.

According to a another embodiment of the present invention, thecompositions can be used to form stable dispersions in the form of awater-in-oil (W/O) or oil-in-water (O/W) emulsion, which comprise: afatty phase, as described supra, in a proportion of from about 0.1 toabout 50% by weight relative to the total weight of the emulsion; anaqueous phase in a proportion of from about 50 to about 98.9% by weightrelative to the total weight of the emulsion, said aqueous phasecontaining biologically-derived 1,3-propanediol, in a proportion of fromabout 1% to about 5% by weight relative to the total weight of theemulsion; and at least one emulsifier in a proportion of from about 1 toabout 10% by weight relative to the total weight of the emulsion.Suitable emulsifiers are well known in the field of cosmetic products.For example, water-in-oil emulsifiers include, but are not limited to,sterols such as cholesterol and its associated esters and alcohols,lanolin, calcium oleate and other fatty acid soaps of divalent metals,beeswax, and polyhydric alcoholics of fatty acids such as glycerylmonostearate and sorbitan sesquioleate. Suitable oil-in-wateremulsifiers include, but are not limited to, ordinary soaps, partiallysulfated fatty alcohols, Cetomacrogol B.P., polyethoxylated esters knownas Spans, cetydimethylbenzyl ammonium chloride, and gums and gumsubstitutes

These emulsions, which are in the form of creams, have good film-formingproperties and give a very satisfactory sensation after they have beenapplied. Such emulsions can be used as skin care, skin cleansing, ormake-up products. When these compositions are skin care products, theycan be anti-wrinkle products for improving the appearance of the skin.When these compositions are make-up products, they may be foundations ormascaras, containing a certain proportion of the pigments and/or dyesdescribed supra.

In another embodiment of the present invention, the personal carecompositions are hair care compositions. Hair care compositions areherein defined as compositions for the treatment of hair, including butnot limited to shampoos, conditioners, hair treatment creams, aerosols,gels, hair sprays, set lotions, blow styling lotions, hair relaxingcompositions, and mousses. The hair care compositions of the presentinvention comprise an effective amount of biologically-derived1,3-propanediol in a cosmetically acceptable medium. An effective amountof biologically-derived 1,3-propanediol for use in a hair carecomposition is herein defined as a proportion of from about 1% to about30% by weight relative to the total weight of the composition.Components of a cosmetically acceptable medium for hair carecompositions are described by Omura et al. in U.S. Pat. No. 6,139,851and Cannell et al. in U.S. Pat. No. 6,013,250, both of which areincorporated herein by reference. For example, these hair carecompositions can be aqueous, alcoholic or aqueous-alcoholic solutions,the alcohol preferably being a monohydric alcohol such as ethanol orisopropanol, in a proportion of from about 1 to about 75% by weightrelative to the total weight for the aqueous-alcoholic solutions. Thehair care compositions may also contain other polyhydric alcoholsincluding, but not limited to, ethylene glycol, propylene glycol,1,3-butylene glycol, glycerine, sorbitol, 2-methyl-1,3-propanediol, andpolyethylene glycol. Additionally, the hair care compositions maycontain one or more conventional cosmetic or dermatological additives oradjuvants, as described supra.

The viscosity of the various personal care compositions depends on thenature of the composition. For example, emulsions typically have aviscosity up to about 250,000 cps. Other cosmetic compositions haveviscosity up to about 600,000, cps, but preferably up to 300,000 cps andmore preferable, up to 250,000 cps. Water thin compositions, for examplesprays or some conditioners, have a viscosity of less than about 100cps.

The present invention also comprises a method for forming a protectivefilm on skin or hair by applying one of the compositions described abovecomprising biologically-derived 1,3-propanediol to the skin or hair andallowing the formation of the protective film. The compositions of thepresent invention may be applied to the skin or hair by various means,including, but not limited to, spraying, brushing, and applying by hand.The composition is left in contact with the skin or hair for a period oftime sufficient to form the protective film, preferably for at leastabout 0.1 to 60 min.

Though the presently disclosed personal care compositions typically havehuman application, personal care compositions for other animals,particularly mammals, more particularly canine, feline, or equine, arealso within the scope of the present disclosure.

Uses of esters from bio-derived 1,3-propanediol in personal careproducts

The monoesters and diesters of bio-derived 1,3-propanediol are useful ina variety of applications.

Esters as described herein are suitable, in a non-limiting way, for usein the composition of liquid hand soaps, shampoos and liquid detergentsas emulisifers, pearlizing agents, surfactants, gelling agents,structurants, thickeners, or opacifiers. The esters containing about 1to about 24 carbons in the alkyl chain are particularly useful in liquidsoap, shampoo and detergent applications.

The esters of the present invention are also useful as an activeingredient in cosmetics as emollients. In other cosmetic applicationssuch esters are useful in the deliver, application or effectiveness ofthe cosmetic. In this use the esters act as an additive or adjuvant.Specifically, in a non-limiting way, such esters can be uses as ahumectant, opacifier, pearlizing agent, gelling agent, emulsifier,surfactant, structurant, thickener, compatibilizer or solvent forcosmetics and personal care products. The fatty acid esters of thepresent invention, containing about 8 to about 24 carbons in the alkylchain are particularly useful in cosmetic applications.

Such esters are also useful as a solvent for botanical products. Suchbotanical products include, but are not limited to, all plants, theirseeds, stems, roots, flowers, leaves, pollen, spices and oils.

Esters as described herein can also be used in inks as an emulsifier incosmetic inks like tattoos or henna dyes.

Such esters are useful in preparation of solid or near solid personalcare products such as stick deodorants and bronzing sticks.

The esters of the present invention are also useful in personal carecompositions as an emulsifier, humectant, gelling agent, surfactant,structurant, thickener, compatibilizer or solvent.

Such personal care applications can be directs to any animal, especiallyavians, reptiles and mammals. The preferred applications are directed tohumans, canine, feline and equine species. The most preferredapplications are directed to human species.

Detergent Compositions

As mentioned above, 1,3-propanediol can be incorporated into numerouscompositions as a glycol component. For example, 1,3-propanediol can bepart of or the sole glycol component of detergent compositions.

In liquid detergent compositions, the glycol component typically is anemulsifier and/or phase stabilizer or a solvent. Exemplary liquiddetergents include, but are not limited to, hand or machine dish washingdetergent, laundry detergent, clothing softener, and car wash detergent.Glycols are present in the aforementioned detergent compositions inamounts well known to those of ordinary skill in the appropriate art,typically up to about 20% by weight based on the weight of the totalcomposition. A typical formulation may include, but is not limited to,the following components by weight percent: 0.0-20.0% glycol, 5.0-40.0%fatty acid ester, and 1.0 to 50.0% surfactant or surfactant blend.Additionally, up to 5.0% by weight of the following components may beincluded: suds stabilizer, pH buffer, and enzymes.

Detergent Compositions Comprising 1,3-propanediol Esters

Esters as describe herein are also suitable, in a non-limiting way, foruse in the composition of liquid soaps and liquid detergents asemulisifers, pearlizing agents, surfactants, gelling agents,structurant, thickener, or opacifier. The esters containing about 1 toabout 24 carbons in the alkyl chain are particularly useful in liquiddetergent applications.

Such liquid soaps and liquid detergents can be directs to any animal,especially avians, reptiles and mammals. The preferred applications aredirected to humans, canine, feline and equine species. The mostpreferred applications are directed to human species.

In addition, the esters of the instant application may used for powderdetergents, such as powder dishwasher detergent, and textilesdetergents.

Such esters are also useful as a solvent for botanical products indetergents. Such detergent compositions comprising botanical productsinclude botanicals directed to plants, their seeds, stems, roots,flowers, leaves, pollen, spices and oils.

The esters in the detergent compositions described herein may alsofunction as an antimicrobial agent.

A further description of types of detergent formulations comprisingfatty acid esters can be found in “Liquid Detergents” (SurfactantScience Series Volume 129, Taylor & Francis Group, Boca Raton, Fla.,2005). Additional description follows, including reference to light-dutyand heavy-duty detergents, both of which are the subject of thedetergents compositions provided herein.

Light-duty liquid detergents are for dishwashing (by hand) and liquiddetergents for textile, delicate garments—usually the exposure times arerelatively short, about 20 minutes and the use concentrations are low,about 0.15%. Esters in these compositions provide benefit as non-ionicsurfactants.

Heavy-duty liquid detergents (HDLD) are for textile applications (forwashing machines). In this context the fatty acid esters are mostly thenon-ionic surfactants. The non-ionic surfactants (beside the anionicsurfactants) are primarily responsible for wetting the surfaces offabrics as well as the soil (reducing surface and interfacial tension),helping to lift the stains off the fabric surface, and stabilizing dirtparticles and/or emulsifying grease droplets. Esters in thesecompositions provide additional benefits as aesthetic ingredients andhelp to create a microemulsion.

TABLE 1 General formulation of a Structured HDLD: Ingredient Function %Sodium Linear Alkylbenzene Anionic surfactant  0-30 Sulfonate SodiumAlkyl Ether Sulfate Anionic surfactant  0-10 Alcohol Ethoxylate Nonionicsurfactant  0-10 Sodium Carbonate Builder  0-25 Zeolite Builder  0-25Sodium Perborate Bleach  0.0-10.0 Polymer Stabilizer 0.0-1.0 ProteaseEnzyme 0.0-1.5 Fluorescent Whitening Agent Brightener 0.0-0.5 Boric Acid0.0-5.0 Preservative 0.05-0.2  Fragrance 0.0-0.6 Colorant 0.00-0.2 

TABLE 2 General formulation of an Unstructured HDLD: Ingredient Function% Sodium Linear Alkylbenzene Anionic surfactant 0-15  Sulfonate SodioumAlkyl Ether Sulfate Anionic surfactant 0-15  Alcohol Ethoxylate Nonionicsurfactant 0-15  Sodium Citrate Builder 0-10  Monoethanolamine Buffer0-5   Soap Defoamer 0-5   Protease Enzyme 0-1.5 Fluorescent WhiteningAgent Brightener 0-0.5 Boric Acid Enzyme stabilizer 0-5.0 EthanolSolvent 0.0-5 Sodium Xylene Sulfonate Hydrotrope  0-10.0 Preservative0.05-0.2  Fragrance 0-0.6 Colorant 0-0.2

The fatty acid esters of the instant invention may also function asnon-ionic cosofteners. Generally glycol fatty acid esters deliver goodsoftness and static control without any drawback.

Other type of detergents within the instant invention include creamcleaners, as it has been found that fatty acid esters provide formicroemulsion characteristics that benefit cream cleaners or detergents.Gel cleaners maybe formulated within the instant invention for the samereasons.

EXAMPLES

The present invention is further defined in the following Examples. Itshould be understood that these Examples, while indicating preferredembodiments of the invention, are given by way of illustration only.From the above discussion and these Examples, one skilled in the art canascertain the essential characteristics of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various uses andconditions.

All ingredients used in the preparation of the personal carecompositions described in the following Examples are availablecommercially unless otherwise noted.

The meaning of abbreviations used is as follows “% wt.” means percent byweight; “qs” means as much as suffices; “EDTA” means ethylenediaminetetraacetate; “° C.” means degrees Centigrade; “° F.” is degreesFahrenheit, “Bio-PDO” means biologically-derived 1,3-propanediol; “ppm”is parts per million; “AU” is absorbance unit; “nm” is nanometer(s);“GC” is gas chromatograph; “APHA” is American Public Health Association;“cps” is centipoise; “f/t” is freeze/thaw; “mPa·s” is milliPascalseconds; “D.I.” is deionized.

General Methods:

Standard recombinant DNA and molecular cloning techniques used in theExamples are well known in the art and are described by Sambrook, J.,Fritsch, E. F. and Maniatis, T., Molecular Cloning: A Laboratory Manual,Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., 1989, byT. J. Silhavy, M. L. Bennan, and L. W. Enquist, Experiments with GeneFusions, Cold Spring Harbor Laboratory, Cold Spring Harbor, N.Y., 1984,and by Ausubel, F. M. et al., Current Protocols in Molecular Biology,Greene Publishing Assoc. and Wiley-Interscience, N.Y., 1987.

Materials and methods suitable for the maintenance and growth ofbacterial cultures are also well known in the art. Techniques suitablefor use in the following Examples may be found in Manual of Methods forGeneral Bacteriology, Phillipp Gerhardt, R. G. E. Murray, Ralph N.Costilow, Eugene W. Nester, Willis A. Wood, Noel R. Krieg and G. BriggsPhillips, eds., American Society for Microbiology, Washington, D.C.,1994, or by Thomas D. Brock in Biotechnology: A Textbook of IndustrialMicrobiology, Second Edition, Sinauer Associates, Inc., Sunderland,Mass., 1989.

All reagents, restriction enzymes and materials used for the growth andmaintenance of bacterial cells were obtained from Aldrich Chemicals(Milwaukee, Wis.), BD Diagnostic Systems (Sparks, Md.), LifeTechnologies (Rockville, Md.), or Sigma Chemical Company (St. Louis,Mo.), unless otherwise specified.

Glycerol used in the production of 1,3-propanediol was obtained from J.T. Baker Glycerin USP grade, Lot 325608 and G19657.

Differential Scanning calorimetry: DSC thermograms were recorded usingUniversal V3 1A TA instrument under constant stream of nitrogen with aheating and cooling rate of 10° C./min.

NMR: 1H NMR spectra were recorded on Bruker DRX 500 using XWINNMRversion 3.5 software. Data was acquired using a 90 degree pulse (p1) anda 30 second recycle delay (d1). Samples were dissolved in deuteratedchloroform and nondeuterated chloroform was used as internal standard.

Isolation and Identification Bio-PDO

The conversion of glycerol to bio-PDO was monitored by HPLC. Analyseswere performed using standard techniques and materials available to oneof skill in the art of chromatography. One suitable method utilized aWaters Maxima 820 HPLC system using UV (210 nm) and RI detection.Samples were injected onto a Shodex SH-1011 column (8 mm×300 mm,purchased from Waters, Milford, Mass.) equipped with a Shodex SH-1011Pprecolumn (6 mm×50 mm), temperature controlled at 50° C., using 0.01NH2SO4 as mobile phase at a flow rate of 0.5 mL/min. When quantitativeanalysis was desired, samples were prepared with a known amount oftrimethylacetic acid as external standard. Typically, the retentiontimes of glycerol (RI detection), 1,3-propanediol (RI detection), andtrimethylacetic acid (UV and RI detection) were 20.67 min, 26.08 min,and 35.03 min, respectively.

Production of bio-PDO was confirmed by GC/MS. Analyses were performedusing standard techniques and materials available to one of skill in theart of GC/MS. One suitable method utilized a Hewlett Packard 5890 SeriesII gas chromatograph coupled to a Hewlett Packard 5971 Series massselective detector (EI) and a HP-INNOWax column (30 m length, 0.25 mmi.d., 0.25 micron film thickness). The retention time and mass spectrumof 1,3-propanediol generated from glycerol were compared to that ofauthentic 1,3-propanediol (m/e: 57, 58).

Production of Bio-Based Monoesters and Diesters from Bio-Produced1,3-propanediol.

Monoesters and diester of bio-produced 1,3-propandiol may be produced bycombining bioPDO with organic acid. The combination is to be preformedin dry conditions under heat and prolong agitation with a selectedcatalyst. The ratio of monoester to diester produced will vary accordingto the molar ratio of acid to bioPDO and the selection of catalyst.

The production of esters was confirmed using ¹H nuclear magneticresonance. Analyses were performed using standard techniques andmaterials available to one of skill in the art of ¹H NMR.

Proton Nuclear Magnetic Resonance (¹H NMR) Spectroscopy is a powerfulmethod used in the determination of the structure of unknown organiccompounds. It provides information concerning: the number of differenttypes of hydrogens present in the molecule, the electronic environmentof the different types of hydrogens and the number of hydrogen“neighbor” a hydrogen has.

The hydrogens bound to carbons attached to electron withdrawing groupstend to resonate at higher frequencies from TMS, tetramethylsilane, acommon NMR standard. The position of where a particular hydrogen atomresonates relative to TMS is called its chemical shift (δ). Typicalchemicals shifts of fatty ester are as follows.

δ=0.88 for terminal CH₃

δ=1.26, 1.61 and 1.97 for methylene groups of (—CH₂—CH ₂—CH₂), (CH₂—CH₂—C═O) and (O—CH₂—CH ₂—CH₂—O) respectively,

δ=2.28 for methylene group adjustcent to ester (CH ₂—C═O)

δ=4.15 for ester (C(═O)—O—CH ₂—).

Proton NMR can distinguish the protons corresponding to the end groups(CH ₂—OH) (δ=3.7) from that of the middle ester groups (CH ₂—O—C(═O)—)(δ=4.15 and 4.24 for diester and monoester, respectively) and thus it ispossible to identify ester and can monitor the reaction by comparing theintegral areas of these two peaks.

${\%\mspace{14mu}{Esterification}} = \frac{{Combined}\mspace{14mu}{areas}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.15\mspace{14mu}{and}\mspace{14mu} 4.24X\; 100}{{{Combined}\mspace{14mu}{areas}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 3.70},{41.5\mspace{14mu}{and}\mspace{14mu} 4.24}}$

Example 1 Conversion of D-Glucose to 1,3-Propanediol Under FermentationConditions

E. coli strain ECL707, containing the K. pneumoniae dha regulon cosmidspKP1 or pKP2, the K. pneumoniae pdu operon pKP4, or the Supercos vectoralone, is grown in a 5 L Applikon fermenter for the production of1,3-propanediol from glucose.

The medium used contains 50-100 mM potassium phosphate buffer, pH 7.5,40 mM (NH4)2SO4, 0.1% (w/v) yeast extract, 10 μM CoCl2, 6.5 μM CuCl2,100 μM FeCl3, 18μ □M FeSO4, 5 μM H3BO3, 50 μM MnCl2, 0.1 μM Na2MoO4, 25μM ZnCl2, 0.82 mM MgSO4, 0.9 mM CaCl2, and 10-20 g/L glucose. Additionalglucose is fed, with residual glucose maintained in excess. Temperatureis controlled at 37° C. and pH controlled at 7.5 with 5N KOH or NaOH.Appropriate antibiotics are included for plasmid maintenance. Foranaerobic fermentations, 0.1 vvm nitrogen is sparged through thereactor; when the dO setpoint was 5%, 1 vvm air is sparged through thereactor and the medium is supplemented with vitamin B12.

Titers of 1,3-propanediol (g/L) range from 8.1 to 10.9. Yields ofbio-PDO (g/g) range from 4% to 17%.

Example 2 Purification of Biosourced 1,3-Propanediol

Published U.S. Patent Application No. 2005/0069997 discloses a processfor purifying 1,3-propanediol from the fermentation broth of a culturedE. coli that has been bioengineered to synthesize 1,3-propanediol fromsugar. The basic process entails filtration, ion exchange anddistillation of the fermentation broth product stream, preferablyincluding chemical reduction of the product during the distillationprocedure.

1,3-Propanediol, produced as recited in Example 1, was purified, by amultistep process including broth clarification, rotary evaporation,anion exchange and multiple distillation of the supernatant.

At the end of the fermentation, the broth was clarified using acombination of centrifugation and membrane filtration for cellseparation, followed by ultrafiltration through a 1000 MW membrane. Theclarified broth processed in a large rotary evaporator. Approximately 46pounds of feed material (21,000 grams) were processed to a concentratedsyrup. A 60 ml portion of syrup was placed in the still pot of a 1″diameter distillation column. Distillation was conducted at a vacuum of25 inches of mercury. A reflux ratio of approximately 1 was usedthroughout the distillation. Several distillate cuts were taken, thecentral of which received further processing. The material was dilutedwith an equal volume of water, the material was loaded onto an anionexchange column (mixed bed, 80 grams of NM-60 resin), which had beenwater-washed. Water was pumped at a rate of 2 ml/min, with fractionsbeing collected every 9 minutes. Odd number fractions were analyzed, andfractions 3 through 9 contained 3G. The fractions containing 3G werecollected and subjected to microdistillation to recover several grams ofpure 1,3-propanediol monomer (which was polymerized to mono and diestersaccording the methods described in Example 2-8).

Example 3 Production of Propanediol Distearate Using P-ToluenesulfonicAcid As Catalyst

To prepare propanediol distearate from biosource 1,3-propanediol andstearic acid, biosource 1,3-propanediol was purified using methods as inexamples 1 and 2. 2.58 g (0.033 moles) of biosource 1,3-propanediol,19.45 g (0.065 moles) of stearic acid (Aldrich, 95%), and 0.2125 g(0.001 moles) of p-toluenesulfonic acid (Aldrich 98.5%) were chargedinto glass reactor fitted with mechanical stirrer and the reactor wasflushed with dry nitrogen gas to remove air and moisture for 15 min.Then reaction temperature was raised to 100° C. while thoroughlystirring the reaction mixture under nitrogen flow and continued for 210min.

After completion of the reaction, reaction mixture was cooled to about35° C. and the product was transferred into a beaker. The product waspurified by adding 100 mL of water and thoroughly stirring at 45-60° C.,to form an emulsion for 15 min. The mixture was cooled and the solidpropanediol distearate was separated by filtration.

The product was characterized by ¹H NMR (Nuclear Magnetic Resonance)spectra (CDCl₃ (deuterated chloroform)): δ=0.88 (t, CH ₃—CH₂, 6H), 1.26(t, CH₂—CH ₂—CH₂, 28H), 1.61 (t, CH ₂—CH₂—C═O, 4H), 1.97 (t, —O—CH₂—CH₂—CH₂—O, 2H), 2.28 (t, CH ₂—C═O, 4H), 4.15 (t, C(═O)—O—CH ₂— 4H) and DSC(T_(m)=66.4° C. and Tc=54.7° C.).

Example 4 Purity Characterizations of Biologically-Derived1,3-Propanediol

In Table 1 below, biologically-derived 1,3-propanediol (produced andpurified as described in Published U.S. Patent Application No.2005/0069997) (“Bio-PDO”) is compared, in several purity aspects, to twoseparate commercially-obtained preparations of chemically-produced1,3-propanediol (Source A and B).

TABLE 1 Units Source A Source B Bio-PDO Total Org Impurities ppm 570 69580 UV Abs 220 nm, AU 0.25 1.15 0.12 UV Abs 250 nm, AU 0.123 0.427 0.017UV Abs 275 nm AU 0.068 0.151 0.036 UV Abs 350 nm AU 0.013 0.007 0.001Peroxides ppm 67 43 2 CIE L*a*b* ASTM D6290 b* 0.411 0.03 0.1 Carbonylsppm 147 175 1

A typical profile of purity aspects are provided in Table 2 below, on asample of biologically-produced 1,3-propanediol purified by a processdisclosed in Published U.S. Patent Application No. 2005/0069997.

TABLE 2 Units 1,3-Propanediol GC area % 99.992 pH, neat pH 8.22 UV Abs.@ 270 nm, 1:5 dilution AU 0.01 Color APHA 3 Color (Process Measurement)L*a*b* b* 0.10 Water ppm 115 UV abs 220 nm neat AU 0.144 UV abs 250 nmneat AU 0.017 UV abs 275 nm neat AU 0.036 UV abs 350 nm neat AU 0.001Peroxide ppm 2 Metals ppm <1 Sulfur ppm <1 Carbonyl ppm 1

The unit ppm of total organic impurities means parts per million oftotal organic compounds in the final preparation, other than1,3-propanediol, as measured by a gas chromatograph with a flameionization detector. Results are reported by peak area. A flameionization detector is insensitive to water, so the total impurity isthe sum of all non 1,3-propanediol organic peaks (area %) ratioed to thesum of all area % (1,3-propanediol included). The term “organicmaterials” refers to the contaminants containing carbon.

The tables show that the disclosed method of purification provides forhighly pure biologically derived 1,3-propanediol, as compared tocommercially-obtained preparations of chemically-produced1,3-propanediol.

Example 5 Skin Irritation and Sensitization Characterization ofBiologically-Derived 1,3-Propanediol

In a human skin patch test with approximately 100 subjects, 5, 25, and50% PDO did not cause any skin reactions indicative of irritation orsensitization. A second human skin patch test did not produce anyclinically significant dermal irritation or sensitization reactions withconcentrations of 25, 50, and 75% PDO at pH 7, or 75% PDO at pH 4 and 9.Based on these studies PDO is not expected to be a skin irritant orsensitizer in humans. In the second human skin patch test, propyleneglycol (1,2-propanediol or PG) was also tested at 25, 50, and 75% (pH 7)and all three concentrations of PG were patch test irritants andcumulative irritants for human skin.

Examples 6-8 are prophetic and are based on a descriptions from:D'Amelio, Frank S Sr.; Botanicals: A Phytocosmetic Desk Reference; CRCPress 1999, pg. 299-304.

Example 6 A Natural, High Foaming, Gentle Shampoo for Everyday Use

Percent Sequence Raw Material INCI Name 1.00 1 Deionized Water Water0.00 1 Saponins Saponins 0.00 1 Cocamidopropyl Betaine CocamidopropylBetaine .00 1 Cocamide DEA 1:1 Cocamide DEA .10 1 Horsetail Extract,Horsetail Extract 5:1 BIO-PDO .10 1 Comfrey Leaf Extract, Comfrey Leaf5:1 BIO-PDO Extract .10 1 Rosemary Extract, Rosemary Extract 5:1 BIO-PDO.10 1 Chamomile Extract, Matricaria Extract 5:1 BIO-PDO .s. 2 50% Aq.Sodium Sodium Hydroxide Hydroxide .50 3 Aculyn 22 Thickener¹Acrylates/Steareth-20 Methacrylate Copolymer 5.00 4 Plantaren 2000²Decyl Polyglucose .10 Lipovol A³ Avacado Oil .s. 5 25% Aqueous CitricAcid Citric Acid 0.00 6 UCARE Polymer LR 30M Polyquaternium-10 (1.3%)⁴.00 7 Lipamide MEAA⁴ Acetamide MEA Note: 5:1 Bio-PDO is defined as 5parts biologically derived 1,3-propanediol with 1 part dehydratedbotanical. (20% of a 1:1 extract) ¹Rohm & Haas ²Henkel ³Lipo Chemicals,Inc. ⁴Amerchol

Procedure:

-   -   1. Combine Sequence 1 ingredients at room temperature using a        slow to moderate mixing to prevent aeration until homogeneous.    -   2. Adjust pH to 9.2 with Sequence 2 ingredient.    -   3. Slowly add Sequence 3 and continue mixing until polymer is        completely dispersed.    -   4. Add Sequence 4 ingredients slowly and mix until homogeneous.    -   5. Adjust pH to 5.5 with Sequence 5 ingredient.    -   6. Add Sequence 6 slowly and mix until homogeneous.    -   7. Add Sequence 7 slowly and mix until homogeneous.

Example 7 All Natural Blooming Bath Oil

Percent Sequence Raw Material INCI Name 15.96 1 Lipovol ALM⁵ SweetAlmond Oil 63.54 1 Lipovol SES¹ Sesame Oil 5.00 1 Lipolan R¹ Lanolin Oil5.00 1 Lipopeg 2-DL PEG-4 Dilaurate 10.00 1 Lipocol 0-2¹ Oleth-2 0.10 1Propylparaben Propylparaben 0.10 1 Vitamin E USP-FCC⁶ Vitamin E 0.10 2Arnica 5:1 BIO-PDO Arnica Extract 0.10 2 Chamomile 5:1 BIO-PDO ChamomileExtract 0.10 2 Comfrey 5:1 BIO-PDO Comfrey Extract q.s. 3 D & C Green #6(0.5% Sol'n D & C Green #6 in BIO-PDO) Note: 5:1 Bio-PDO is defined as 5parts biologically derived 1,3-propanediol with 1 part dehydratedbotanical. (20% of a 1:1 extract) ⁵Lipo Chemicals, Inc. ⁶Roche Vitaminsand Fine Chemicals

Procedure:

-   -   1. Combine Sequence 1 ingredients under vigorous mixing and heat        to 557° C. until propylparaben is completely dissolved. Cool to        30° C.    -   2. At 30° C., add Sequence 2 ingredients to batch and cool to        25° C. At 25° C., add Sequence 3 until desired shade is        obtained.

Example 8 High Humectant, Aqueous Spray-On Moisturizer

Percent Sequence Raw Material INCI Name 92.70 1 Deionized Water Water2.00 1 Lipocare HA/EC⁷ Echinacin 5.00 1 Liponic EG-1¹ Glycereth-26 0.101 Slippery Elm Bark 5:1 BIO- Slippery Elm PDO⁸ Extract 0.10 1 ChamomileExtract 5:1 BIO- Matricaria Extract PDO² 0.10 1 Wild Alum Extract 5:1BIO- Cranesbill Extract PDO² Note: 5:1 Bio-PDO is defined as 5 partsbiologically derived 1,3-propanediol with 1 part dehydrated botanical.(20% of a 1:1 extract) ⁷Lipo Chemicals, Inc. ⁸BioBotanica/LipoChemicals, Inc.

Procedure:

Combine ingredients under vigorous mixing at room temperature untilbatch is clear and uniform.

Example 9 Extraction of Chamomile Flower Powder by Bio-PDO and Bio-PDOEster Mixture

Esters based on biologically-derived 1,3-propanediol were synthesized,purified and characterized as it is described in U.S. Provisional Patentapplication 60/772,112, filed Feb. 10, 2006, incorporated herein byreference.

Biologically-derived 1,3-propanediol and 1,3-propanediol conjugate esterwere used for the extraction of Chamomile flower powder (Martricariarecutita from Egypt, distributor—Mountain Rose Herbs, Oreg.).

The Chamomile powder was mixed with 1,3-propanediol and macerated for 30minutes on a shaking table, then 1,3-propanediol ester was added to themixture and the temperature was raised to 90° C. and the maceration wascontinued for additional 2 hours. The material was filtered through a0.2 μm GHP membrane and the filtrate was analyzed by LC/MS and shown tocontain extracted compounds.

Example 10 Extraction of Chamomile Flower Powder by Bio-PDO Ester

The biologically-derived 1,3-propanediol conjugate ester was synthesizedas it is written in Example 9 and the ester (Bio-PDO bis-ethylhexanoate)was used for the extraction of Chamomile flower powder (Mountain RoseHerbs, Oreg.).

The Chamomile powder was mixed with the ester and macerated for 2, 4, 6hours on a shaking table. The material was filtered through a 0.2 μm GHPmembrane and the filtrate was analyzed by UV/VIS (UV/VisSpectrophotometer, Varian (Australia), Model: Cary 5000) and the spectrademonstrated that the efficacy of the extracted compounds wasproportional with the time used for the maceration.

Example 11 Extraction of Red Roses by Bio-PDO Ester

The biologically-derived 1,3-propanediol conjugate ester was synthesizedas it is written in Example 9 and the ester (Bio-PDO bis-ethylhexanoate)was used for the extraction of dried Red Roses (Rosa centifolia,Mountain Rose Herbs, Oreg.).

The dried roses was mixed with the ester and macerated for 2, 4, 6 hourson a shaking table. The material was filtered through a 0.2 μm GHPmembrane and the filtrate was analyzed by UV/VIS.

Example 12 Extraction of Seaweed by Bio-PDO Ester

The biologically-derived 1,3-propanediol conjugate ester was synthesizedas it is written in Example 9 and the ester (Bio-PDO bis-ethylhexanoate)was used for the extraction of dried seaweed (local farmers' market).

The dried seaweed was mixed with the ester and macerated for 2, 4, 6hours on a shaking table. The material was filtered through a 0.2 μm GHPmembrane and the filtrate was analyzed by UV/VIS.

Example 13 Botanical Extraction Using Bio-PDO/Methanol Mixture

Procedure: 5 g of dried Jasmine flower (Jasminum officinale, MountainRose Herbs, Oreg.) was immersed in the mixture of Bio-PDO/methanol(70%:30%) and macerated for 24 h. The material was filtered through a0.2 μm GHP membrane and the filtrate was analyzed by LC/MS. The LC/MSspectra demonstrated the effective extraction of the active ingredients.

Example 14 Honeysuckle Flower Extraction Using Bio-PDO/Deionized WaterMixture

Procedure: 5 g of dried Honeysuckle flower (Lonicera japonica, originChina, distributor Mountain Rose Herbs, Oreg.) was immersed in themixture of Bio-PDO/d.water (50%:50%) and macerated for 24 h. Thematerial was filtered through a 0.2 μm GHP membrane and the filtrate wasanalyzed by LC/MS. The LC/MS spectra demonstrated the effectiveextraction of the active ingredients.

Example 15 Eucalyptus Leaf Extraction Using Bio-PDO/Deionized WaterMixture

Procedure: 5 g of dried Eucalyptus leaf (Eucalyptus globulus, originFrance, distributor Mountain Rose Herbs, Oreg.) was immersed in themixture of Bio-PDO/d.water (50%:50%) and macerated for 24 h. Thematerial was filtered through a 0.2 μm GHP membrane and the filtrate wasanalyzed by LC/MS. The LC/MS spectra demonstrated the effectiveextraction of the active ingredients.

Example 16 Sandalwood Red Powder Extraction Using Bio-PDO/DeionizedWater Mixture

Procedure: 5 g of dried Sandalwood Red Powder (Pterocarpus santalinus,origin Africa, distributor Mountain Rose Herbs, Oreg.) was immersed inthe mixture of Bio-PDO/d.water (50%:50%) and macerated for 24 h. Thematerial was filtered through a 0.2 μm GHP membrane and the filtrate wasanalyzed by LC/MS. The LC/MS spectra demonstrated the effectiveextraction of the active ingredients.

Comparative Example 1 Comparison Between Biologically Derived1,3-Propanediol and Propylene Glycol in Plant Material Extractions

Bio-1,3-propanediol and propylene glycol were used to extractingredients from Jasmine flower, Chamomile flower powder (Matricariarecutita) myrrh gum cut benzoin gum powder, and bees wax. LC-MS andGC-MS were used to analyze the extracted ingredients. Qualitativeanalysis confirmed that ingredients extracted using 1,3-propanediol aresame as those extracted using propylene glycol. Additionally,ingredients extracted using bio-1,3-propanediol and mixtures ofbio-1,3-propanediol and methanol were the same.

The major ingredients of chamomile extraction are bisabolol oxide,en-in-dicyclo ether, and Apigenin glucoside. Comparitive yields of theseactive ingredients using 1,3-propanediol and propylene glycol(1,2-Propanediol, Aldrich) are shown below in Table 1:

TABLE 1 Bio-1,3-propanediol Propylene Extract Product Area Glycol Area %difference Bisabolol oxide 9217821^(a) 8760424^(a) 5.2 Apigeninglucoside 3972525^(b) 3549734^(b) 11.2 en-in-dicyclo ethers 9394370^(b)7261956^(b) 29.2 ^(a)GC-MS analysis, ^(b)LC-MS analysis

The table shows the GC-MS/LC-MS peak areas of the extracted ingredientsusing 1,3-propanediol and propylene glycol. Using Bio-1,3-propanediolthe extraction process extracted 29.4 wt % higher en-in-cycloethers,11.2 wt % higher apigenin glucoside, and 5.2 wt % higher bisabolol oxideas compared to the extraction using propylene glycol.

Comparative Example 2

Chamomile flower powder (5 g) was mixed with 50 g of solvent mixture(Bio-PDO/Deionized Water, ratio 1:1, and also the mixture of1,2-Propanediol (Propylene glycol, Aldrich)/Deionized Water, ratio 1:1).The mixture was kept for agitation for 24 h. The extract was filteredand analyzed.

TABLE 2 Comparison of extraction of Chamomile using Bio-PDO andPropylene glycol Bio-PDO/ Propylene glycol/ Product Water Area WaterArea % Difference Bisabolol oxide 25176422 14409166 75 Apigenin 2374215556691 326 Apigenin glucoside 658824 420412 57 en-in-dicyclo ethers1842764 866635 113

The data in Table 2. show the GC-MS/LC-MS peak areas of the extractedingredients using Bio-PDO/water and propylene glycol/water mixtures.Using Bio-PDO/water mixture 75 wt % higher Bisabolol oxide, 326 wt %higher Apigenin, 113 wt % higher en-in-cycloethers, 57 wt % higherapigenin glucoside were extracted than those extracted using propyleneglycol.

Comparative Example 3

Hamomile flower powder (Mountain Rose Herb, Oreg.) (5 g) was mixed with50 g of Bio-PDO also 5 g of Chamomile flower powder was mixed withDeionized Water. The mixture was macerated for 24 h. The extract wasfiltered and analyzed by LC/MS.

TABLE 3 Comparison of extraction of Chamomile using Bio-PDO and WaterProduct Bio-PDO/Area H₂O/Area % Difference Apigenin 63.32 125.53 −50.4Apigenin glucoside 134.58 0 en-in-dicyclo ethers 1340.74 0

Using deionized water apigenin glucoside and en-in-dicyclo ethers werenot extracted though apigenin extraction was higher compared to thatusing Bio-PDO.

Example 17 Biologically-Derived 1,3-Propanediol in Cosmetic Emulsion

Ingredients: % Wt. Phase A Water, deionized 61.34 Tetrasodium EDTA 0.10Bio-PDO ™ (E.I. du Pont de Nemours 5.00 and Company (“DuPont”),Wilmington, Del.) Carbopol 980 (2% solution) 10.00 Phase B Puresyn ®25.00 Lipomulse ® 165 2.50 Stearic Acid XXX 2.50 Cetearyl Alcohol 0.50Dimethicone DC 200-100 1.00 Phase C NaOH (20% solution) qs to pH 7.0-7.51.06 Phase D Germaben II 1.00

Phase A was combined at 75° C. Phase B was combined at 75° C. Phase Bwas added to Phase A. Phase C was then added to the Phase A/B. PhaseA/B/C was cooled to 40° C. and then Phase D was added. pH was adjustedto 7.0-7.5 with Phase C. The formulation produced was a smooth white andapparently stable emulsion.

RESULTS—pH 7.38, viscosity 12000 cps at 20 RPM. Oven stability wasexamined. Results were deemed acceptable. Freeze/thaw stability was alsoexamined. Freeze/thaw stability was deemed acceptable.

Comparative Examples 4-6 Cosmetic Emulsions Containing Other Polyols

For comparative purposes, cosmetic emulsions containing other polyolswere also produced as described in Example 17, except that thebiologically-derived 1,3-propanediol was substituted with propyleneglycol, 1,3-butylene glycol, or 2-methyl-1,3-propanediol. The cosmeticemulsions containing propylene glycol, 1,3-butylene glycol, or2-methyl-1,3-propanediol were stable.

The viscosity of the cosmetic emulsion containing biologically-derived1,3-propanediol was on par with that of propylene glycol (12600 cps) andhigher than that of 1,3-butylene glycol (6000 cps) or2-methyl-1,3-propanediol (9600 cps).

Example 18 Skin Irritation Characterization of Biologically-Derived1,3-Propanediol

The purpose of this study was to determine the potential ofbiologically-derived 1,3-propanediol, diluted to concentrations of 5%,25%, and 50%, to cause irritation or delayed contact hypersensitivity inhumans. The method employed in carrying out this test, described below,was similar to that described in “Appraisal of the Safety of Chemicalsin Foods, Drugs and Cosmetics” by J. H. Drake and published by theAssociation of Food and Drug Officials of the United States,incorporated herein by reference.

Test Panel: The test involved the application of the test article to theupper arms of a group of 112 volunteer panelists. The panelists rangedfrom 16 to 71 years of age. One hundred and five panelists completed thestudy. Prior to the initiation of the study, all panelists were in goodgeneral health and free of any visible skin disease or anomaly in thearea to be patched. Each panelist was required to read, understand andsign an informed consent statement.

Patch Preparation: The test articles (biologically-derived1,3-propanediol diluted with D.I. water to a concentration of 5%,diluted with D.I. water to a concentration of 25%, and diluted with D.I.water to a concentration of 50%) were applied (0.1 mL) to a one-inchLintine® Disk (Filter Fabrics, Goshen, Md.) and placed onto a strip of 2inch Dermicel® hypoallergenic cloth tape (Johnson & Johnson, NewBrunswick, N.J.). Before applying this strip, each portion of testmaterial was secured in place with a gloved finger to insure properapplication. This tape strip was then pressed into place on the upperleft arm of each panelist at its designated test site.

Induction Phase: These patches were applied to their designated contactsites and remained in place for 24 hours. At the end of this period, thepatches were removed and the sites were examined for any dermalresponse. The panelists were then rested for a 24-hour period afterwhich the skin sites were again examined. New patches were then appliedto the same sites as previously used. The second applications wereidentical to the first and remained in place 24 hours. This procedurewas repeated on Mondays, Wednesdays and Fridays until a series of nineapplications had been made. Patch applications made on Friday wereremoved by the panelists on Saturday. The panelists examined the sites(with assistance if necessary) for any dermal response at the time ofremoval and again at 48 hours and reported their observations prior tothe next application. The same sites were used throughout the study. Inthe event when one induction application was missed, the panelist wasallowed to make it up at the end of the induction patch period. Thesepatches were applied on Monday following the last scheduled (ninth)induction application on Friday.

Challenge Phase: After the 9th application, a rest period ofapproximately 2 weeks elapsed after which a challenge application wasapplied in the same manner and to the same sites described above.

Based upon the effects observed with the test materials placedrepeatedly on the skin during both the induction and challenge phases,biologically-derived 1,3-propanediol, diluted to concentrations of 5%,25%, and 50%, is considered not to be a skin irritant, fatiguing agent,or sensitizing agent under the conditions that prevailed in this study.

Example 19 Clear Face and Hand Lotion

Ingredients: % Wt. Deionized water 66.20 Bio-PDO ™ (DuPont) 16.00Ritasail 190 (RITA) (dimethicone copolyol) 2.00 Pationic ® 122A (RITA)(sodium caproyl lactylate 3.80 21.1% aqueous) Rhodapex ® ESY (Rhodia)(sodium laureth sulfate 4.00 26% aqueous) Germaben II (ISP/Sutton)(propylene glycol, diazolidinyl urea, 1.00 methylparaben andpropylparaben) Tetrasodium EDTA 5% aqueous 1.00 Aculyn ® 22 (ISP/Rohm &Haas) (acrylates/steareth-20 5.00 methacrylate copolymer 25% aqueous)Triethanolamine 1.00 Fragrance q.s.

Procedure: Ingredients are combined in order as listed. Properties: pH:7.0, viscosity: 6,780 cps

Example 20 Hand and Body Cream

Ingredients: % Wt. Deionized water 75.49 Cellosize ® PCG 10 (Amerchol)0.20 Trisodium EDTA (Universal Preserv-A-Chem) 0.10 Bio-PDO ™ (DuPont)6.50 Shebu ® Refined (RITA) (shea butter) 2.00 Arlacel ® 60 (Uniqema)4.00 MYRJ ® 52S (Uniqema) 0.50 Glycol stearate (Stepan) 2.00 DC SF200/350 (Dow Corning) 4.00 Isopropyl palmitate (Stepan) 3.00 Vitamin Apalmitate (Roche) 0.01 Aloe vera gel (Bio-Botanica) 0.50 Cucumberextract (Bio-Botanica) 0.50 Ginkgo biloba extract (Bio-Botanica) 0.50Red clover extract (Bio-Botanica) 0.50 Biopein ® (Bio-Botanica) 0.20

Procedure: Disperse Cellosize® PCG 10 into deionized water with mixing.Add trisodium EDTA and Bio-PDO™ with mixing and heat to 80° C. Add thenext seven items and continue mixing until uniform. Remove heat andallow to cool. At 30° C., add aloe vera gel, cucumber extract, ginkgobiloba extract and red clover extract. Add Biopein® and mix untilhomogenous.

Example 21 Moisturizing Body Care Cream

Ingredients: % Wt. Phase A Cremophor ® A6 (BASF) (ceteareth-6) 2.0Cremophor ® A25 (BASF) (ceteareth-25) 2.0 Vitis vinifera (grape) seedoil 6.0 Glyceryl Stearate SE 3.0 Cetearyl alcohol 2.0 Dimethicone 0.5Luvitol EHO (BASF) (cetearyl octanoate) 8.0 Oxynex ® 2004 (Merck KgaA)(1,3-Propanediol, BHT, 0.1 ascorbyl palmitate, glyceryl stearate andcitric acid) Phase B Bio-PDO ™ (DuPont) 5.0 Edeta BD (BASF) (disodiumEDTA) 0.1 D-Panthenol USP (BASF) 1.0 Preservative q.s. Water q.s. to 100Phase C Luvigel EM (BASF) (caprylic/capric triglycerides and 1.0 sodiumacrylates copolymer) Phase D Vitamin E Acetate (BASF) 0.5 Perfume q.s.

Procedure: Heat phase A and phase B to about 80° C. Stir phase B intophase A while homogenizing. Add phase C to phase A/B and homogenizeagain. Cool to about 40° C., add phase D and homogenize shortly.Properties: Viscosity: approx. 25,000 mPa·s (Brookfield); pH value: 6.5

Example 22 Moisturizing Body Care Cream

Ingredients: % Wt. Phase A Cremophor ® GC 7 (BASF) (PEG7-glyceryl-cocoate) 8.0 Cremophor ® A-25 (BASF) (ceteareth-25) 22.0Cremophor ® WO 7 (BASF) (hydrogenated castor oil) 1.0 Bio-PDO ™ (DuPont)3.0 Masil ® SF19 (BASF) (PEG 8 methicone) 1.0 Phase B Water 65.0 Phase CPreservative q.s. Fragrance q.s.

Procedure: Add ingredients in above order at 80° C. and mix untiluniform. Assure each is dissolved prior to next addition. Heat phase Bto 80° C. and combine with phase A. Cool to 50° C. Add fragrance andpreservative. Pour into containers while liquid and allow to set at roomtemperature.

Example 23 Moisturizing Hand and Body Lotion

Ingredients: % Wt. Phase A Varisoft ® TA-100 (Goldschmidt) 4.75(distearyldimonium chloride) Crodacol C-70 (Croda) (cetyl alcohol) 2.00Penreco Snow White Petrolatum (Penreco) (petrolatum) 4.00 DC Fluid 200,1,000 cst (Dow Corning) (dimethicone) 0.25 Phase B Deionized water q.s.Stepan ® IPM (Stepan) (isopropyl myristate) 3.25 Bio-PDO ™ (DuPont) 4.00Phase C Sensomer ® CI-50 (Ondeo Nalco) (starch 3.00hydroxypropyltrimonium chloride) AA040513 Cucumber (Arylessence)(fragrance) 0.25 Preservative q.s. Sodium hydroxide q.s. to pH 6

Procedure: In separate containers, thoroughly mix the ingredients ofphase A and phase B to 75° C. Pour phase A into phase B; mix well attemperature for 10 minutes. Remove heat and continue mixing untiltemperature is under 40° C. Add phase C ingredients in the order listed,mixing well between additions. Adjust pH to 6.

Example 24 Moisturizing Lotion SPF15

Ingredients: % Wt. Phase A Stearyl alcohol 2.00 Estol ® 1543 (Uniqema)(ethylhexyl palmitate) 5.00 Estol ® 3609 (Uniqema) (triethylhexanoin)5.00 Tween ® 60 (polysorbate 60) 2.00 Isohexadecane 7.50 Solaveil ®CT100 (Uniqema) (C12-C15 alkyl benzoate (and) 15.00 titanium dioxide(and) polyhydroxystearic acid (and) aluminum stearate (and) alumina)Phase B Distilled water 54.40 Arlatone ® 2121 (Uniqema) (sorbitanstearate (and) sucrose 2.50 cocoate) Monomate RMEA-40 (aqua (and)disodium ricinoleamido 0.200 MEA-sulfosuccinate) Phase C Veegum ® Ultra(RT Vanderbilt) (magnesium aluminum 0.80 silicate) Keltrol ® RD(Nutrosweet Kelco) (xanthan gum) 0.20 Sodium lactate 50% 0.40 Germaben ®II (ISP) (propylene glycol (and) diazolidinyl urea 1.00 (and)methylparaben (and) propylparaben) Bio-PDO ™ (DuPont) 4.00

Procedure: Heat phase B to 80° C. with moderate stirring, untilArlatone® 2121 is fully dispersed. Add Keltrol® and Veegum®; stir untilhomogeneous. Add remaining water phase ingredients, maintainingtemperature at 80° C. Heat phase A to 80° C. Add phase A to B/C withvigorous mixing. Homogenize for two minutes. Cool with moderate stirringto room temperature.

Example 25 Skin Treatment Lotion

Ingredients: % Wt. Phase A Deionized water 61.7 Keltrol ® CG (Kelco)(xanthan gum) 0.2 Bio-PDO ™ (DuPont) 5.0 Multifruit ® BSC (Arch PersonalCare) 3.0 Jeescreen Benzophenone-4 (Jeen) (benzophenone-4) 0.1 JeechemGMS-165 (Jeen) (glyceryl stearate (and) PEG-100 3.0 stearate) Phase BJeesilc IDD (Jeen) (dimethicone crosspolymer-3 (and) 4.0 isododecane)Jeesilc 245 (Jeen) (cyclomethicone) 8.0 Jeesilc 200 MV (100 cst)(dimethicone) 2.0 Simulgel ® NS (Seppic) 4.0 Phase C Jeesilc 6056 (Jeen)(dimethylpolysiloxane gum) 3.0 Jeecide G-II (Jeen) (propylene glycol(and) diazolidinyl urea 1.0 (and) methylparaben (and) propylparaben)Arnica Extract (Botanicals Plus) (arnica montana) 2.0 Flamingo Super Red1.0 Phase D Jeesorb L-20 (Jeen) (polysorbate 20) 1.0 Vitamin E Acetate(Jeen) (tocopheryl acetate) 0.5 Fragrance 0.5

Procedure: Heat water to 65° C. Pre-mix Keltrol® and Bio-PDO™ and add tothe water phase. Mix until dissolved. Add the other ingredients of phaseA one at a time and mix well. Cool to 50° C. In the oil phase tank, addthe Jeesilc IDD, Jeesilc 245 and Jeesilc 200 MV (100 cst) and mix untiluniform. Add the Simulgel® and mix to 50° C. Using a homogenizer, addphase B to phase A and mix for 10 minutes. Cool to 40° C. Switch to propagitation. Add the ingredients of phase C one at a time into the maintank and mix well after each addition. Pre-mix phase D in a side vesseland add to the main tank. Mix well.

Example 26 Broad Spectrum SPF Sunscreen

Ingredients: % Wt. Phase A Deionized water 57.85 Carbopol 980 (Noveon)(carbomer) 0.30 Disodium EDTA (Dow Chemical) 0.10 Bio-PDO ™ (DuPont)4.00 Phase B Escalol 557 (ISP) (octinoxate) 7.50 Escalol 567 (ISP)(oxybenzone) 6.00 Escalol 517 (ISP) (avobenzone) 2.00 X-Tend 226 (ISP)(2-phenylethyl benzoate) 10.00 Prolipid ® 141 (ISP) (glyceryl stearate,behenyl 4.00 alcohol, palmitic acid, stearic acid, lecithin, laurylalcohol, myristyl alcohol and cetyl alcohol) Phase C Deionized water5.00 Triethanolamine 99% 0.40 Phase D Liquapar Optima (ISP)(phenoxyethanol, methylparaben, 1.25 isopropylparaben, isobutylparabenand butylparaben) Liquapar Oil (ISP) (isopropylparaben, isobutylparaben0.40 and butylparaben) Lexguard O (Inolex) (caprylyl glycol) 1.00 PhaseE Glycacil ®-L (Lonza) (iodopropynyl butylcarbamate) 0.20

Procedure: Combine ingredients in phase A; mix until uniform and heat to75° C. Combine ingredients in phase B; heat to 75° C. Combine phase Bwith phase A with homogenization. Combine phase C with phase A/B withhomogenization. Cool to 45° C. (heat Lexguard O and add to LiquaParOptima) and add phase D. Add phase E. Cool to room temperature. Qs forwater loss.

Properties: Viscosity: 17,600 cps, pH 6.44

Example 27 Water-Resistant Sunscreen Lotion SPF 21

Ingredients: % Wt. Phase A Deionized water 63.10 Versene ® NA (Dow)(disodium EDTA) 0.05 Carbopol Ultrez 10 Polymer (Noveon) (carbomer) 0.25Pemulen ® TR-2 Polymeric Emulsifier (Noveon) 0.15 (acrylates/C10-30alkyl acrylate crosspolymer) Bio-PDO ™ (DuPont) 3.00 Phase BNeoHeliopan, Type AV (Haarmann & Reimer) 5.00 (octyl methoxycinnamate)Octyl salicylate 3.00 HallBrite ® BHB (C.P. Hall) (butyloctylsalicylate) 5.00 Parsol ® 1789 (Roche) (avobenzone) 3.00 Procol CS-20-D(Protameen) (cetearyl alcohol and ceteareth-20) 1.50 Crodamol CAP(Croda) (cetearyl octanoate) 2.00 Vitamin E acetate (BASF) 0.50 Phase CCrovol A-70 (Croda) (PEG-60 almond glycerides) 0.50 DC 1401 Fluid (DowCorning) (dimethiconol and 1.50 cyclomethicone) Ultrasil Copolyol-1Silicone (Noveon) (PEG-8 dimethicone) 1.50 Phenonip ® (Clariant)(phenoxyethanol, methylparaben, 1.00 ethylparaben, propylparaben,butylparaben and isobutylparaben) Tapioca Pure (National Starch)(tapioca starch) 4.00 Sodium hydroxide 18% 1.00 Avalure ® UR 450 Polymer(Noveon) 3.95 (PPG-17/IPDI/DMPA copolymer 38% solids)

Procedure: Dissolve disodium EDTA in warm water (−50° C.). Add CarbopolUltrez 10 polymer and allow to wet out for approximately five minutes.Disperse Pemulen® Polymeric emulsifier and allow to mix in for about 15minutes. Add Bio-PDO™. Bring phase A to ˜70° C. Add approximately 15% ofthe total neutralizing agent necessary to phase A. Blend phase Bingredients and bring to ˜80° C., making sure solid ingredients aredissolved. Add phase B to phase A with vigorous agitation. Add PEG-60almond glycerides. Add dimethiconol and cyclomethicone. Add UltrasilCopolyol-1 silicone. Add Phenonip® after the emulsion cools to <60° C.Add tapioca starch. Add the remainder of the neutralizing agent. AddAvalure® UR 450 polymer.

Properties: Appearance: white, creamy emulsion

pH: 7.0-7.5

Viscosity (mPa·s)*: 15,000-21,000

SPF (waterproof)**: 21 (in-vitro method, 80 min. immersion)

Example 28 Waterproof Protective Suncare SPF 20

Ingredients: % Wt. Phase A Simusol 165 (Seppic) (glyceryl stearate andPEG-100 stearate) 3.20 Montanov ® S (Seppic) (coco-glucoside and 1.30coconut alcohol) Isodecyl neopentanoate 10.00 PVP hexadecene copolymer5.00 Bio-PDO ™ (DuPont) 5.00 Ethyl hexyl methoxycinnamate 7.50Benzophenone-3 2.50 Ethyl hexyl salicylate 5.00 Zinc oxide 7.10 Phase BSepicalm VG (Seppic) (sodium palmitoyl proline and 3.00 Nymphea albaflower extract) Cyclomethicone 5.00 Phase C Simulgel ® EG (Seppic)(sodium acrylate/ 1.00 acryloyldimethyltaurate copolymer, isohexadecaneand polysorbate 80) Phase D Tromethamine q.s. Tetrasodium EDTA 0.20Xanthan gum 0.15 Magnesium aluminum silicate 1.00 Water q.s. to 100Phase E Sepicide HB (Seppic) (phenoxyethanol (and) methylparaben 0.30(and) ethylparaben (and) propylparaben (and) butylparaben) Sepicide CI(Seppic) (imidazolidinyl urea) 0.20 DL-alpha tocopherol 0.05 Fragrance0.30

Procedure: Melt phase A ingredients at 75-80° C. and disperse zinc oxidein the warm fatty phase. Disperse silicate and xanthan gum in wateruntil homogeneous, then introduce EDTA and tromethamine. Add Simulgel®EG to this blend with vigorous stirring to obtain swelling of thepolymer, then heat to 80° C. Add fatty phase A to the water phase andbegin homogenizing for five minutes. Start cooling while continuouslyhomogenizing. Introduce Sepicalm VG and cyclomethicone at 60° C. andhomogenize for five minutes. Cool with moderate stirring and add phase Eingredients at 30° C.

Example 29 Hand Barrier Cream

Ingredients: % Wt. Phase 1 D.I. Water q.s. to 100.0 Bio-PDO ™ (DuPont)4.00 Ammonyx ® GA-70PG* 2.86 Phase 2 Petrolatum 4.00 Stepan ® IPP 3.00Stepan ® Cetyl Alcohol, NF 2.00 TiO2Sperse 40% solution in OctyldodecylNeopentanoate 10.00 (Collaborative Labs) Phase 3 KCl 0.40 Citric Acidq.s. Preservatives q.s. Total 100.00

Procedure: Prepare water phase by adding water, Bio-PDO™ and Ammonyx®GA-70PG*. Mix well. Start heating to 160° F. Prepare oil phase by addingPetrolatum, Stepan® IPP, Stepan® Cetyl Alcohol and TiO2Sperse. Heat to160-165° F. Add oil phase to the water phase. Emulsify for 20-25minutes. Cool to room temperature. Premix KCl with water and add tobatch. Add preservatives. Adjust pH to 4.0 if necessary.

Physical Properties 4.0-5.0; 2,000-3,000 cps

Example 30 Lotion for Normal-Oily Skin

Ingredients: % Wt. Phase 1 D.I. Water q.s. to 100.0 Carbopol 934 (BFGoodrich) Carbomer 0.15 Bio-PDO ™ (DuPont) 3.00 Phase 2 Stepan ® OctylIsononanoate 5.00 Dow Corning 200 Fluid (Dow Corning) Dimethicone 0.10Wecobee ® S 0.50 Stepan ® Cetyl Alcohol, NF 0.50 Kartacid 1890 (AkzoNobel BV) Stearic Acid 3.00 Phase 3 Versene ® 200 (Dow Corning)Tetrasodium EDTA 0.10 Triethanolamine 1.80 Preservative q.s. Total 100.0

Procedure: Prepare Phase 1 by adding D.I. water to a suitable mixingvessel and begin agitation. Add Carbopol 934 with good agitation and mixat high speed until the solution is free of lumps. Add Bio-PDO™ and mix.Heat to 165-170° F. In a separate container prepare Phase 2 and heat to170-175° F. Add Phase 2 to Phase 1 with good agitation and mix for 30minutes. Start cooling to 90° F. At 110° F. add Phase 3 ingredients.Stop cooling and agitation at 90° F.

Properties: Viscosity at 25° C.: 2000-5000 cps; pH 7.8-8.0

Example 31 Skin Soothing Lotion

Ingredients: % Wt. Phase 1 D.I. Water q.s. to 100.0 Carbopol 940 (B.F.Goodrich) Carbomer 0.20 Glucam ® P-20 (Amerchol) PPG-20 Methyl GlucoseEther 0.14 Bio-PDO ™ (DuPont) 2.25 Phase 2 Neobee ® M-20 4.50 Wecobee ®S 0.75 Stepan ® 653 0.50 Stepan ® Cetyl Alcohol, NF 0.50 Kartacid 1890(Akzo Nobel BV) Stearic Acid 2.95 Phase 3 Preservative 0.10 Versene ®220 (Dow) Tetrasodium EDTA 0.10 Triethanolamine 0.25 Total 100.0

Procedure: Prepare Phase 1. Add Carbopol 940 to D.I. water with goodmixing until solution is free of lumps. Add PPG-20 methyl glucose etherand Bio-PDO™. Mix until completely dissolved. Heat to 165° F. In aseparate container, prepare Phase 2. Heat to 165-170° F. Add Phase 2 toPhase 1 (both at 165-170° F.) with good agitation. Emulsify for 20minutes and then begin to cool with slow agitation. At 110° F. addingredients from Phase 3. At 90° F. stop cooling and agitation.

Properties: Viscosity: at 25° C.: 2200-3700 cps

Example 32 Clear Moisturizer

Ingredients: % Wt. Aloe Vera Gel q.s. to 100.0 Bio-PDO ™ (DuPont) 3.50Methyl Paraben 0.15 Carbopol 934 0.50 Alcohol 190 Proof 20.00 Stepan ®PEG 600 ML 1.00 Tween ® 2.00 Fragrance q.s. TEA 88% 0.8 Glydant q.s.Total 100.0

Procedure: Combine Aloe Vera Gel and Bio-PDO™. Start mixing. Add methylparaben. Mix until solution is clear. Add Carbopol 934. Mix untilsolution does not have lumps. Add alcohol. Mix well. Premix PEG 600Monolaurate, Tween 20 and perfume. Add to batch. Mix well. Add Glydant.Add TEA. Solution should be clear.

Physical Properties: pH 6.0-6.5

Example 33 Therapeutic Hand & Body Lotion

Ingredients: % Wt. Phase 1 D.I. Water q.s. to 100.0 Bio-PDO ™ (DuPont)4.00 Ammonyx ® GA-70PG 18.4 Phase 2 Petrolatum 4.0 Stepan ® IPP 3.0Silicone DC-200 (350 cps) 1.0 Stepan ® Cetyl Alcohol, NF 2.0 Phase 3 KCl0.4 Citric Acid q.s. Glydant q.s. Total 100.0

Procedure: Prepare water phase by adding water, Bio-PDO™, and Ammonyx®GA-70PG. Mix well. Start heating to 160° F. Prepare oil phase by addingpetrolatum, Stepan® IPP, silicone, Stepan® Cetyl Alcohol. Heat to160-165° F. Add oil phase to water phase. Emulsify for 20-25 minutes.Start cooling. Premix KCl with water and add into the batch at 100-110°F. Add Glydant at 100° F. Adjust pH if necessary. Homogenize ifnecessary.

Physical Properties: pH 4.0-4.5; viscosity: 3,000-4,000 cps

Example 34 Cream Conditioner for Permanent Waved Hair

Ingredients: % Wt. Ammonyx ® 4 5.00 Bio-PDO ™ (DuPont) 1.50 Panthenol0.50 Citric Acid q.s. D.I. Water q.s. to 100 Stepan ® Cetyl Alcohol, NF2.50 PPG-Ceteth 20 1.25 Stepan ® Stearyl Alcohol 97 0.75 Fragrance, Dye& Preservative q.s. Total 100.0  

Procedure: Add ingredients and mix while heating to 75° C. Mix untilwell blended. Cool with mixing to 30° C. and add fragrance,preservative, and dye if desired. Adjust pH with citric acid to 3-5.

Physical Properties: Opaque, white liquid; 2000 cps

Example 35 Clear Hair Conditioner

Ingredients: % Wt. Ammonyx ® KP 3.00 Ammonyx ® CETAC 1.50 Bio-PDO ™(DuPont) 1.50 Hydroxyethylcellulose 0.90 Polyquaternium 10 0.25Fragrance, Dye & Preservative q.s. Citric Acid q.s. D.I. Water q.s. to100 Total 100.0  

Procedure: Disperse hydroxyethylcellulose in D.I. water with mixinguntil clear. Add Ammonyx® KP and mix until homogeneous. Slowly addAmmonyx® CETAC and mix until homogeneous. Disperse Polyquaternium-10 inBio-PDO™ and add to above solution with mixing until clear. Adjust pH to5.5, if necessary, with citric acid. Add fragrance, dye andpreservative, if desired.

Physical Properties: pH 5.5; viscosity: 750 cps

Example 36 Spray-On Detangling Conditioner

Ingredients: % Wt. D.I. Water q.s. to 100.0 Bio-PDO ™ (DuPont) 1.50Ammonyx ® KP 1.00 Surfactant 193 (Dow Corning) 1.00 Dimethicone CopolyolTween ® 20 (ICI) Polysorbate-20 0.30 Citric Acid (50%) q.s. Fragrance,Dye & Preservative q.s. Total 100.0  

Procedure: Into a vessel equipped with agitation, add first fouringredients. Mix well. Premix fragrance and Tween® 20 in a separatecontainer. Add to the batch. Mix well. Adjust pH with citric acid, ifnecessary. Add dye and preservative as desired.

Physical Properties: pH 4.0-4.4; Viscosity at 25° C.: water thin

Example 37 Moisturizing Spray

Ingredients: % Wt. Water 70.8 Preservative 0.2 Bio-PDO ™ (DuPont) 28.0Ammonyx ® GA-70PG 0.9 Hydrolyzed Silk 0.1 Fragrance 0.1 Total 100.0

Procedure: Charge water. Add Bio-PDO™. Heat to 50° C. and blend inAmmonyx® GA-70PG. Mix well until homogeneous. Cool with mixing. At 30°C., add propyl paraben and hydrolyzed silk. Cool to 25° C., addfragrance. Adjust pH to 5.5-6.5 with citric acid or sodium hydroxide.

Physical Properties: Viscosity: 20 cps

Example 38 Men's After Shave Clear Microemulsion

Ingredients: % Wt. Phase 1 Stepan ® PEG 400 MO 12.7 Stepan ® IPM 11.0Stepan ® PEG 400 ML 7.0 Bio-PDO ™ (DuPont) 3.5 Stepan ® GMO 3.0 DC 556Silicone Fluid (Dow Corning) 1.0 Phase 2 Ethanol 25.0 Triethanolamineq.s. Fragrance, dye, preservative q.s. D.I. Water q.s. to 100 Total100.0

Procedure: Heat D.I. water to 95° C. Mix the components of Phase (1) andheat to 95° C. Add Phase (1) to D.I. water with mixing. Cool to 30° C.,and add ethanol. Adjust pH to 7.0-8.0 with triethanolamine. Addfragrance, dye, and preservative, if desired. This formula will create aclear microemulsion.

Physical Properties: pH 7.0-8.0; viscosity: 40 cps

Example 39 Foundation

# SEQ. INGREDIENT NMN2-43-1 NMN2-43-2 NMN2-43-3 1 A Deionized Water63.00 63.00 63.00 2 A CMC 7H3SF 0.30 0.30 0.30 3 A Veegum Ultra Granules0.35 0.35 0.35 4 A Alcolec S (Lecithin) 0.40 0.40 0.40 5 ATriethanolamine 99% 1.25 1.25 1.25 6 A Propylene Glycol 6.00 — — 7 AButylene Glycol — 6.00 — 8 A Bio-PDO ™ (1,3-Propanediol) — — 6.00 9 BTitanium Dioxide (water 8.00 8.00 8.00 dispersible) 10 B Red Iron Oxide0.40 0.40 0.40 11 B Yellow Iron Oxide 0.80 0.80 0.80 12 B Black IronOxide 0.10 0.10 0.10 13 B Colloidal Kaolin 2.00 2.00 2.00 14 B MethylParaben 0.20 0.20 0.20 15 C Permethyl ® 102A (Isoeicosane) 10.00 10.0010.00 16 C Isostearic Acid 1.00 1.00 1.00 17 C Stearic Acid TriplePressed 2.50 2.50 2.50 18 C LIPO GMS 450 (Glyceryl 1.50 1.50 1.50Monostearate) 19 C Liponate TDTM (Tridecyl 1.00 1.00 1.00 Trimelitate)20 C LIPO GMS 470 (Glyceryl 1.00 1.00 1.00 Monostearate) 21 C PropylParaben 0.20 0.20 0.20 FORMULA TOTALS 100.00 100.00 100.00

The manufacturing procedure for this emulsion was typical for alloil-in-water type products. Sequence A was dispersed and when the gumswere completely hydrated and the phase was uniform, pre-ground SequenceB (pigment phase) was added to it and mixed until both phases werecompletely uniform and homogeneous. Sequence C was weighed in a separatevessel and heated to 75°-80° C. until all the solids were melted and thephase was uniform. Sequence A was then heated to 75°-80° C. When all thephases were all at the proper temperatures, Sequence C (oil phase) wasslowly added to Sequences A & B (water phase). The emulsion was allowedto mix at 75° C. for 15 minutes and then cooled to 25° C. Samples fortesting were then poured off and placed at their respective stabilitystations in preparation for the 4 week study. The color and powder fillloading in these formulations was kept constant at 11.30% dry pigment.Conventional powder fill ingredients were chosen for these formulationsas to eliminate any potential variability in test results.

Physical Testing:

Brookfield Model RV - Spindle 5 at 20 rpm for 1 minute (factor × 200)Initial Initial 1 Week 2 Week 2 Week 3 Week 4 Week 4 Week pH ViscosityViscosity pH Viscosity Viscosity pH Viscosity NMN2- 7.95 2900 3100 8.023100 3100 7.99 3100 43-1 NMN2- 8.03 2900 3100 8.00 3200 3300 8.04 320043-2 NMN2- 8.03 2400 2900 7.94 2900 2900 8.02 2900 43-3

Viscosity readings throughout the 4 week test period showed that therewas no unusual build or decrease in viscosity. Oven stability consistedof R/T, 45° C., and 2 Freeze/Thaw cycles. After 4 weeks, samples showedno signs of separation, sweating, severe loss of viscosity, change inconsistency, loss of structure, odor problems, or color change at anytemperature.

Aesthetic Properties:

All samples were evaluated for potential differences in odor, color,appearance, application, texture, feel, wearability, or any otherdifferences, if any. All foundation samples were evaluated side-by side.In no cases were there any perceivable differences in any of theaesthetic properties associated with these types of cosmetic properties.Any differences noticed were insignificant and were not a result of theingredient changes. These were all fragrance free formulations, andthere were no apparent odor differences in any of the samples.

Example 40 Mascara

# SEQ. INGREDIENT NMN2-44-1 NMN2-44-2 NMN2-44-3 1 A Deionized Water49.00 49.00 49.00 2 A Xanthan Gum 0.15 0.15 0.15 3 A Veegum HV Granules0.55 0.55 0.55 4 A Disodium EDTA 0.05 0.05 0.05 5 A Triethanolamine 99%0.50 0.50 0.50 6 A Alcolec S (Lecithin) 0.20 0.20 0.20 7 A MethylParaben 0.30 0.30 0.30 8 A Propylene Glycol 10.00 — — 9 A ButyleneGlycol — 10.00 — 10 A Bio-PDO ™ (1,3-Propanediol) — — 10.00 11 B BlackIron Oxide 9.00 9.00 9.00 12 C DC 345 Fluid (D5 4.50 4.50 4.50Cyclomethicone) 13 C DC5225C Formulation Aid 0.90 0.90 0.90 14 C WhiteBeeswax 7.25 7.25 7.25 15 C Carnauba Wax #1 3.50 3.50 3.50 16 C StearicAcid Triple Pressed 1.80 1.80 1.80 17 C Lipomulse 165 (Glyceryl 1.801.80 1.80 Monostearate) 18 C Indopol H100 (Polybutene) 3.50 3.50 3.50 19C Phenoxyethanol 1.00 1.00 1.00 20 C Propyl Paraben 0.20 0.20 0.20 21 CPVP/Eicosene Colpolymer 4.00 4.00 4.00 22 C Lipocol S (Stearyl Alcohol)1.80 1.80 1.80 FORMULA TOTALS 100.00 100.00 100.00

The manufacturing procedure for this formula was similar to that of thefoundation in Example 24. Higher temperatures were required for the oilphase due to the high level of hard waxes employed in this product.Sequence A was dispersed and when the gums were completely hydrated andthe phase was uniform, pre-ground sequence B (pigment phase) was addedto it and mixed until both phases were completely uniform andhomogeneous. Sequence C was weighed in a separate vessel and heated to80°-85° C. until all the solids were melted and the phase was uniform.Sequence A was then heated to 75°-80° C. When all the phases were all atthe proper temperatures, Sequence C (oil phase) was slowly added toSequences A & B (water phase). The emulsion was allowed to mix at 75° C.for 15 minutes. When the batch began to thicken at around 45° C., apaddle mixer was used to adequately turn over and mix the batch. Thebatch was mixed and cooled to 35° C. Samples for testing were thenpoured off and placed at their respective stability stations inpreparation for the 4 week study. The color loading in theseformulations was kept constant at 9.00% dry pigment. No other powderfill, except for the black iron oxide pigment, was employed in theseformulations. Additional powder fills will lend to a whitening andashyness, which, in mascaras, is unacceptable.

Physical Testing:

Brookfield Model RV - Spindle T at 5 rpm for 1 minute (factor × 10,000)Initial Initial 1 Week 2 Week 2 Week 3 Week 4 Week 4 Week pH ViscosityViscosity pH Viscosity Viscosity pH Viscosity NMN2- 8.78 140,000 300,0008.76 340,000 360,000 8.75 380,000 44-1 NMN2- 8.48 190,000 370,000 8.43420,000 450,000 8.45 420,000 44-2 NMN2- 8.58 180,000 320,000 8.55380,000 430,000 8.55 420,000 44-3

Viscosity readings throughout the 4 week test period showed that therewas no unusual build or decrease in viscosity. The variations seen arevery typical for a product of this type and fall within an acceptablerange for a mascara type product. Oven stability consisted of R/T, 45°C., and 2 Freeze/Thaw cycles. After 4 weeks, samples showed no signs ofseparation, sweating, severe loss of viscosity, change in consistency,loss of structure, odor problems, or color change at any temperature.

Aesthetic Properties:

All samples were evaluated for potential differences in odor, color,appearance, application, texture, feel, wearability, or any otherdifferences, if any. All mascara samples were evaluated side-by side. Inno cases were there any perceivable differences in any of the aestheticproperties associated with these types of cosmetic properties. Anydifferences noticed were insignificant and were not a result of theingredient changes. Additionally, the mascara samples showed nodifferences in water resistance. Even though the mascara was notspecifically designed to be water resistant, side by side, the productsperformed equally. These were all fragrance free formulations, and therewere no apparent odor differences in any of the samples.

Example 41 Body Wash

Ingredients: % Wt. Water 45.0  Ammonium Lauryl Sulfate, 25% 21.0 Ammonium Laureth Sulfate, 28% 21.0  Cocamidopropyl Betaine, 35% 4.0Acrylates Copolymer, Structure 3001 (30%) 5.0 1,3-Propanediol 1.0Glycerin 1.0 PEG 10 Sunflower Glycerides 0.5 Soybean Oil 0.2 Fragrance(0.2) Cocamide MEA 0.2 PEG 5 Cocamide 0.2 Guar Hydroxypropyl trimoniumChloride 0.2 Diisopropanolamine 0.1 Methylcellulose  0.05 Carbomer  0.05Tetrasodium EDTA  0.05 Methylchloroisothiazolinone,  0.05Methylisothiazolinone Etidronic Acid  0.05 Guanine (CI 75170)  0.05 Mica(CI 77019)  0.05 Titanium Dioxide (CI 77891)  0.05 TOTAL 100   

Ingredients were combined in the following order, with propeller mixeragitation, allowing each ingredient to dissolve, disperse completelybefore adding the next. Batch was processed at 60° C.: Water, Acrylatespolymer, ALS, ALES, GAB, Guar Hydroxypropyl trimonium Chloride, EDTA,PEG 10 Sunflower glycerides, soybean oil, cocamide MEA, PEG 5 cocamide,diisopropanolamine/methylcellulose/carbomer/guanine, mica/titaniumoxide, glycerin.

Example 42 Baby Lotion

Ingredients: % Wt. Water 85.2 1,3-Propanediol 3.0 Myristyl Myristate 2.5Glyceryl Stearate 1.5 Oleic Acid 1.2 Stearic Acid 1.2 Polysorbate 61 0.6C12-15 Alkyl Benzoate 0.5 Dimethicone 0.5 Isopropyl Palmitate 0.5Sorbitan Stearate 0.5 Cetyl Alcohol 0.5 Synthetic Beeswax 0.5 StearylAlcohol 0.5 Benzyl Alcohol 0.4 Carbomer 934 0.4 Fragrance 0.1Methylparaben 0.2 Propylparaben 0.05 Butylparaben 0.05 BHT 0.05 D&C Red3 trace TOTAL 100

Ingredients were combined in the following order, allowing each todissolve/disperse completely before adding the next:

Phase A: Disperse Carbomer in water with high speed agitation, allowingparticles to wet completely. Add 1,3-propanediol. Heat to 70° C.

Phase B: Combine Myristyl Myristate, glyceryl stearate, Oleic Acid,Polysorbate 61, C12-15 Alkyl Benzoate, Dimethicone, Isopropyl Palmitate,Sorbitan Stearate, Cetyl Alcohol, Synthetic Beeswax, Stearyl; Alcohol,Benzyl Alcohol, Methylparaben, Propylparaben, Butylparaben, and BHT,heat to 70° C.

With continuous high speed agitation, slowly add Phase B to Phase A toform emulsion. Remove from heat and begin cooling with continuedagitation. After several minutes of mixing, add NaOH, dissolved in asmall amount of water. Batch will thicken. When Batch reaches roomtemperature, add color, fragrance, and replace water lost toevaporation. Batch is complete.

Example 43 Sulfate-Free Shampoo

Phase Ingredients: % Wt. A Water 33.82 A NA2EDTA 0.05 A BIOTERGE AS 4045.00 A GLUCAMATE DOE 120 1.50 A 1,3-PROPANEDIOL 4.75 B MONAMID CMA 3.00B VELVETEX BK 35 10.00 C KATHON CG 0.06 C MACKPEARL 140V 1.50 D CITRICACID, 20% SOLN 0.32 TO PH 6.0-6.5 TOTAL 100.00

Manufacturing Process:

Phase A: Combine Phase A ingredients into water and heat with mixing to75° C. Slowly add remaining Phase A ingredients. Hold temperature at 75°C. and mix slowly.

Phase B: Combine phase B ingredients and heat to 75° C. with slowmixing. Add Phase B to Phase A and mix until uniform.

Phase C: Add Phase C one at a time

Phase D: Use Phase D to adjust the pH of batch to 6.0-6.5

Example 44 Liquid Powder

Using the present invention liquid powder can be prepared usingbio-based propanediol caprylate. Obtain the ingredients in theproportionate amounts listing in Table 1. Starting with the ingredientsin Table 1, phase A, add inulin lauryl carbamate to water and disperseCARBOPOL ULTREZ 10 (B.F. Goodrich Company, New York, N.Y.). Blend themixture of phase A ingredients for about 10 minutes, until the carbomeris completely dispersed and hydrated. Under light agitation raise thetemperature of the mixture to about 70° C.

In a separate clean container, combine the components listed in Table 1,phase B in the amount stipulated by the table, including bio-basedpropanediol caprylate, and heat to about 75° C. After the componentshave been fully combined and are at the target temperature, slowly addphase B mixture to the phase A mixture. Apply rapid agitation and holdtemperature between about 70° C. and about 75° C. for 30 minutes. After30 minutes allow the combined mixtures to cool to 55° C. and withcontinuous agitation slowly add corn starch of phase C in the amountstipulated by Table 1. When the corn starch has been thoroughly mixedinto the combined ingredients of phases A and B, add fragrance andpreservative of phase C. Adjust the fragrance and preservative asdesired. Measure the pH and then if necessary adjust the pH to betweenabout 5.5 to about 6.0 with triethanolamine. When the pH has beenadjusted, cool to room temperature.

TABLE 1 Ingredients: % WT. Phase A Water 55.7 Inulin lauryl carbamate0.5 Carbopol Ultrez 10 (Carbomer) 0.3 Phase B Neopentyl glycoldiheptanoate and isodecane 5.0 Stearamidopropyl morpholine lactate (25%)2.0 Stearyl benzoate 3.0 Sorbitan oleate 0.5 Bio-based propanediolcaprylate 0.5 Phase C Topical Starch (Corn Products corn starch 037570)30.0 Fragrance q.s. Phenoxyethanol and DMDM hydantoin q.s. Paragon III(Methylparaben and propylparaben q.s. Triethanolamine (99%) q.s. to pH5.5-6.0

Example 45 Pearlized Milk Bath

The present invention can be used to prepare a pearlized milk bath usingbio-based propanediol distearate. Following the percentages in Table 2,combine UCARE polymer LR-400 with a sufficient amount water to hydrate.Then following the percentage listed in Table 2, blend in PLANTOPON 611L (Fitz Chem Corporation, Itasca, Ill.) and LAMESOFT PO 65 (Fitz ChemCorporation, Itasca, Ill.) until the mixture reaches uniformconsistency.

At this point add polymer solution in the amount listed in Table 2 tothe mixture and agitate until uniform consistency is restored. Nextfollowing the percentage listed in Table X, add glycerin, STANDAMOX CAW(Fitz Chem Corporation, Itasca, Ill.), NUTRILAN MILK (Fitz ChemCorporation, Itasca, Ill.), bio-based propanediol distearate and mixwell until the mixture is again of uniform consistency. Measure the pHand if necessary adjust with citric acid to reach a final pH of betweenabout 6 to about 7. Finally add preservative, dye, fragrance and enoughwater to reach the desired volume. The final viscosity of the mixtureshould be between about 5,000 cPs to about 10,000 cPs.

TABLE 2 Ingredients: % WT. Plantopon 611 L (Sodium laureth sulfate andlauryl 22.00 glucosidee and cocamidopropyl betaine) Lamesoft PO 65 (Cocoglucoside and glyceryl oleate) 3.00 Standamox CAW (Cocamidopropylamineoxide) 3.00 Bio-based propanediol distearate 2.00 Nutrilan Milk(Hydrolyzed milk protein) 1.50 Emery 917 (Glycerin) 0.50 Ucare polymerLR-400 (Amerchol) (polyquaterium-10) 0.10 Water, preservative,fragrance, dye q.s.

Example 46 Gentle Baby Shampoo

The present invention can be use in the preparation of a gentle babyshampoo using bio-based propanediol oleate. Obtain the ingredients inthe proportionate amounts listed in Table 3. Heat an amount water ofslight less than required volume according to Table 3, to about 40° C.Add ingredients in the amount and order listed in Table 3. Mix theingredients together with gentle agitation, do not exceed 100 rpm. Whenthe mixture has reached uniform consistency, add water to bring themixture to the desired final volume. The let the mixture cool to roomtemperature. The resulting shampoo is prepared correctly should appearclear and colorless.

TABLE 3 Ingredients: % WT. Deionized water q.s. to 100 Tego Betaine L-7(cocamidopropyl betaine) 18.5 Neosorb 70/20 (sorbitol) 16.9 Plantaren1200 UP (lauryl glucoside) 15.9 Plantaren 818 UP (coco glucoside) 12.5Amisoft LS-11 (sodium lauroyl glutamate) 5.0 Bio-based propanediololeate 2.2 D-panthenol USP (D-panthenol) 1.0 Sensomer CI-50 (Ondeo Nalco0.5 (hydroxypropyltrimonium chloride) Crotein HKP Powder (keratin aminoacid) 0.4 Fragrance 0.1 Preservative q.s.

Example 47 Moisturizing Body Wash

The present application can be used in the preparation of a moisturizingbody wash using bio-based propanediol stearate. To prepare such amoisturizing body wash, start by obtaining the list of ingredients inthe proportional amounts listing in Table 4. Mix the together the sodiumlaureth sulfate, JORDAPON CI (BASF Corporation, Mount Olive, N.J.),AVANEL S150 CGN (BASF Corporation, Mount Olive, N.J.), PEG-150distearate, Cocamidopropyl betaine, Cocamide MEA, and bio-basedpropanediol stearate in approximately half of the total water requiredfor the desired volume. After these ingredients thoroughly combined,apply heat to raise the temperature of the mixture to about 65° C.Maintain a temperature of about 65° C. until all components havedissolved and a uniform mixture is obtained. While allowing the mixtureto cool, add LUVIQUAT PQ 11 (BASF Corporation, Mount Olive, N.J.) andgently agitate.

In a separate container, mix the CREMOPHOR PS20 (BASF Corporation, MountOlive, N.J.), vitamin E acetate and fragrance together until fullyblended. When the temperature of the first mixture has dropped to below40° C., add the mixed the CREMOPHOR PS20 (BASF Corporation, Mount Olive,N.J.), vitamin E acetate and fragrance to the mixture. Next added theD,L-PANTHENOL 50 W (BASF Corporation, Mount Olive, N.J.) to the mixtureand gently agitate until thoroughly blended. Next add the D,L-Panthenol50 W to the mixture and gently agitate until thoroughly blended. Nextadd the disodium EDTA to the mixture and gently agitate until thoroughlyblended. Next, add to the mixture a preservative, selected to beadequate for the expected conditions and shelf-life. Finally, add waterto bring the mixture to the desired volume, and agitate until an evenconsistency is achieved.

TABLE 4 Ingredients: % WT. Deionized water 59.1 Sodium laureth sulfate10.0 JORDAPON CI (sodium cocoyl isethionate) 10.0 AVANEL S150 CGN(sodium C12-15 pareth sulphonate) 3.0 PEG-150 distearate 0.5Cocamidopropyl betaine 8.0 Cocamide MEA 3.0 Bio-based propanediolstearate 2.0 LUVIQUAT PQ11 (polyquaternium-11) 1.0 CREMOPHOR PS20(polysorbate-20) 2.0 D,L-PANTHENOL 50 W (panthenol) 0.5 Vitamin Eacetate 0.1 Fragrance 0.2 Disodium EDTA 0.5 Preservative 0.5

Example 48 Deep Penetrating Hair Reconstructor

The present invention can be used in the preparation of a deeppenetrating hair reconstructor using bio-based propanediol dicaprylate.To prepare such a hair reconstructor obtain the ingredients as listed inand in the relative quantities as depicted in Table 5. Then, mix theDEHYQUART L 80 (Cognis GMBH, Dusseldorf, Del.) CETIOL CC (Cognis GMBH,Dusseldorf, DE), DC 949 (Dow Corning, Midland Mich.), GLUADIN WLM(Cognis GMBH, Dusseldorf, DE), perfume, and preservative, i.e. all thecomponents of table 5, phase A. Agitate the component of phase A untilcompletely homogeneous.

In a separate container, disperse the LAMESOFT PW 45 (Grunau IllertissenGmbH, Illertissen, DE) in a quantity of water as shown in Table 5, phaseB. When LAMESOFT PW 45 has been fully dispersed add it to the phase Amixture.

In a separate container, mix the bio-based propanediol dicaprylate indeionized water in a quantity of water as shown in Table 5, phase Cuntil a homogeneous cream is obtained. Then, add phase A and B to phaseC and agitate until a desire consistency is achieved. If necessaryadjust pH to between about 6.5 and about 7.5 using either citric acid orsodium hydroxide.

Ingredients: % WT. Phase A DEHYQUART L 80 (Dicocoylethylhydroxyethylmonium 2.00 methosulfate and propylene glycol) CETIOL CC(Dicaprylyl carbonate) 1.00 DC 949 (Dow Corning) (Amodimethicone andcetrimonium 1.00 chloride and trideceth-12) GLUADIN WLM (Hydrolizedwheat protein) 2.00 Perfume q.s. Preservative q.s. Phase B LAMESOFT PW45 (Cetyl palmitate and beheneth-10 and 4.00 hydrogenated castor oil andglyceryl stearate) Water 37.75 Phase C Bio-based propanediol dicaprylate2.25 Water 50.00

Example 49 Bronzing Stick

The present invention can be used to prepare a bronzing stick using bothbio-based propandiol myristate and bio-based propanediol diprylate. Toprepare such a bronzing stick, obtain all the ingredients in theproportions indicated in Table 6. Combine PEG-8, tocopherol, ascorbylpalmitate, ascorbic acid and citric acid, i.e. all the ingredients ofTable 6, Phase C and mix together until homogenized. Combine theingredients of Phase C, with the microcrystalline wax SP-1028 (Strahl &Pitsch, Inc., West Babylon, N.Y.), lauryl laurate (Strahl & Pitsch,Inc., West Babylon, N.Y.), microcrystalline wax SP-89 (Strahl & PitschInc., West Babylon, N.Y.), microcrystalline wax SP-19 (Strahl & PitschInc., West Babylon, N.Y.), caprylic/capric triglycerides (Cognis GMBH,Dusseldorf, DE), bio-based propandiol myristate, bio-based propanedioldiprylate, Trioctyldodecyl citrate (Phoenix, Merseyside, UK), andPropylparaben (Spectrum Chemical Manufacturing Corporation, Gardena,Calif.). Mix the combination while heating. Bring the combination toabout 85° C. under continuous agitate. Maintain 85° C. until the mixturehas reached homogeny.

In a separate container, mix together the Colorona bronze cosmeticpigment (Rona Cosmetics GmBH, Darmstadt DE), Timiron MP-10 cosmeticpigment (Rona Cosmetics GmBH, Darmstadt DE), Colorona copper cosmeticpigment (Rona Cosmetics GmBH, Darmstadt DE), and Biron LF-2000 cosmeticpigment (Rona Cosmetics GmBH, Darmstadt DE), i.e. all the components ofTable 6, phase B. When the phase B components have been thoroughlymixed, blend them into the already combined phase A and phase C mixture,while continuing to heat at 85° C. After the phase B mixture has beenthoroughly combined with phase A and phase C and homogeny has reached,allow the mixture to cool to between about 70° C. and about 80° C. Whilethe mixture is between about 70° C. and about 80° C., pour the mixtureinto molds to create sticks. Allow the mixture to fully cool to roomtemperature before removing the formed sticks from the molds.

TABLE 6 Ingredients: % WT. Phase A Microcrystalline wax SP-1028 (Strahl& Pitsch) 11.70 Lauryl laurate (Strahl & Pitsch) 3.00 Microcrystallinewax SP-89 (Strahl & Pitsch) 2.80 Microcrystalline wax SP-19 (Strahl &Pitsch) 2.80 Caprylic/capric triglycerides (Cognis) 14.00 Bio-basedpropanediol myristate 15.00 Bio-based propanediol diprylate 19.40Trioctyldodecyl citrate (Phoenix) 3.00 Propylparaben (Spectrum Chemical)0.20 Phase B Colorona bronze cosmetic pigment (Mica and iron oxides)13.00 Timiron MP-10 cosmetic pigment (Mica and titanium oxides) 3.00Colorona copper cosmetic pigment (Mica and iron oxides) 3.00 BironLF-2000 cosmetic pigment (Bismuth oxychloride) 3.00 Phase C PEG-8 0.02tocopherols 0.02 ascorbyl palmitate 0.02 ascorbic acid 0.02 citric acid0.02

Example 50 Lip Gloss

Mix caster oil, Bio-PDO™ distearate, cetyl alcohol and heat the mixtureto 75° C. until a uniform solution is formed. Add color pigment and heatthe mixture while stirring till no lumps are remained. Add TiO2 and heatto 85° C. with stirring until a uniform product is formed. Add fragrancewhile cooling and transfer into containers.

Ingredients: % WT. Phase A Caster oil 55.0 Bio-PDO ™ distearate 16.0Cetyl alcohol ¹ 1.6 Pigment (iron oxide) ² 1.5 TiO2 25.4 Fragrance QS ¹The Chemistry Store.com, Cayce, SC ² Somerset Cosmetic Co. LLC, Renton,WA

Example 51 Pearlized Milk Bath

Poly(diallyldimethylammonium chloride), 20 wt % in water was blendedwith PLANTOPON 611 L, polyglucoside, Bio-PDO™ oleate and cocamide DMA inthe proportional amounts listed in Table until the mixture reachesuniform consistency. Then glycerin, milk protein, Bio-PDO™ oleate,Bio-PDO™ distearate were added and mixed well until the mixture is againof uniform consistency. Measure the pH and if necessary adjust withcitric acid to reach a final pH of between about 6 to about 7. Finallyadd preservative, dye, fragrance and enough water to reach the desiredvolume. The final viscosity of the mixture should be between about 5,000cPs to about 10,000 cPs.

Ingredients: % WT. Plantopon 611 L³ 22.00 Polyglucose (decyl glucoside)² 3.00 Cocamide DMA¹ 3.00 Bio-PDO ™ oleate 0.50 Bio-PDO ™ distearate2.00 Milk protein 1.50 Glycerin 0.50 Poly (diallyldimethylammonium 1.00chloride), (20 wt % in water)⁴ Water, preservative, fragrance, dye q.s.¹The Chemistry Store.com, Cayce, SC ² Somerset Cosmetic Co. LLC, Renton,WA ³Fitz Chem Corporation, Itasca, IL ⁴Sigma-Aldrich, Milwaukee, WI

Example 52 Moisturizing Body Wash

Mix the together the blend 213 (Chemistry Store), Cocamidopropylbetaine, Cocamide DEA, and Bio-PDO™ distearate. After these ingredientsthoroughly combined, apply heat to raise the temperature of the mixtureto about 70° C. Maintain a temperature of about 70° C. until allcomponents have dissolved and a uniform mixture is obtained. Whileallowing the mixture to cool, add poly(diallyldimethylammonium chloride)solution and gently agitate.

When the temperature of the first mixture has dropped to below 40° C.,add the polysorbate-60, vitamin E acetate to the mixture. Next added thePanthenol to the mixture and gently agitate until thoroughly blended.Next add the disodium EDTA to the mixture and gently agitate untilthoroughly blended. Next, add to the mixture a preservative, fragranceand water to bring the mixture to the desired volume, and agitate untilan even consistency is achieved.

Ingredients: % WT. Blend 213 ¹ 47.0 Sodium Laureth SulfateCocamidopropyl Betaine Cocamide DEA PEG-150 Distearate CocamidopropylBetaine ¹ 4.0 Cocamide DEA ¹ 3.0 Bio-PDO ™ distearate 2.0 Poly(diallyldimethylammonium 5.0 chloride), (20 wt % in water) ⁴Polysorbate-60² 2.0 Panthenol 0.5 Vitamin E acetate 0.1 Disodium EDTA0.5 Preservative 0.5 D.I Water, Fragrance q.s. ¹ The ChemistryStore.com, Cayce, SC ²Somerset Cosmetic Co. LLC, Renton, WA ³ Fitz ChemCorporation, Itasca, IL ⁴ Sigma-Aldrich, Milwaukee, WI

Example 53 Bronzing Stick

Mix the ingredients of Phase A. Heat the mixture to about 70° C. undercontinuous agitation. Maintain 70° C. until the mixture has reachedhomogeneous.

In a separate container, mix together the TiO2, and pigment(s) and blendthem into the phase A mixture, while continuing to heat at 70° C. Afterthe phase B mixture has been thoroughly combined with phase A andhomogeny has reached, allow the mixture to cool to about 50° C., pourthe mixture into molds to create sticks. Allow the mixture to fully coolto room temperature before removing the formed sticks from the molds.

Ingredients: % WT. Phase A Emulsifyin Wax NF ¹ 17.42 Bio-PDO ™distearate 18.13 Bio-PDO ™ dilaurate 14.10 Bio-PDO ™ dicaprylate 19.54Cetyl alcohol ¹ 2.27 Germaben II ¹ 0.20 PEG-8 0.02 Citric acid 0.12Phase B TiO2 25.18 Pigment (Iron oxide) ² 3.02 ¹ The ChemistryStore.com, Cayce, SC ² Somerset Cosmetic Co. LLC, Renton, WA

Example 54 Hand Cleanser

Blend ammonium laury sulfate, cocamide DEA, sodium lauryl sulfatesolution and BioPDO™ at room temperature. Add BioPDO™ stearate andIrgsan. Heat to 60° C. while stirring until solids are dissolved. Coolto 30° C., add EDTA. Stir until a homogeneous solution is formed. Adjustto pH 6 with citric acid. Add fragrance.

Ingredients: % WT. Ammonium Lauryl Sulfate (ALS) (28%) 26.0 Cocamide DEA² 6.0 Sodium Lauryl Sulfate (SLS) (25%) 18.0 Bio-PDO ™ 1 1.0 Water 44.5Bio-PDO ™ stearate 0.5 Irgasan ⁶ 0.2 Tetrasodium EDTA (5 wt %) 2.0Citric acid (50 wt %) QS Fragrance 0.2 ¹ DuPont Tate & Lyle Bio Products² The Chemistry Store.com, Cayce, SC ³ Somerset Cosmetic Co. LLC,Renton, WA ⁴ Stephan Co. Northfield, IL ⁵ Noveon, Cleveland, OH ⁶Sigma-Aldrich, Milwaukee, WI

Example 55 Sunscreen

Combine components of phase A mix and heat to 75° C. In a separatecontainer mix the components of phase B and heat to 75° C. Combine phaseB with phase A. Cool it to 45° C. Add components of phase C. Mix itthoroughly. Add components of phase D and E. Mix it until viscositydeveloped.

Ingredients: % WT. Phase A Deionized water 58.01 Carbopol 934 (Noveon,Cleveland, OH) 0.40 Disodium EDTA 0.125 Bio-PDO ™ 4.00 Phase BOxybenzone ³ 15.50 Phenylethyl benzoate 10.00 Bio-PDO ™ stearate 2.00Ceteareth ³ 2.00 Phase C Deionized water 5.00 TEA 0.50 Phase D GermabenII ² 1.65 Bio-PDO ™ ¹ 0.50 Phase E Idopropynyl butylcarbamate 0.20 pH: 7Viscosity: 12700 @ 30 rpm ¹ DuPont Tate & Lyle Bio Products ² TheChemistry Store.com, Cayce, SC ³ Somerset Cosmetic Co. LLC, Renton, WA ⁴Stephan Co. Northfield, IL ⁵ Noveon, Cleveland, OH ⁶ Sigma-Aldrich,Milwaukee, WI

Example 56 Liquid Automatic Dishwashing Detergent

Ingredients Wt. % Water 54.30 Citric Acid 5.93 Bio-PDO ™ (DuPont) 6.92Carbopol ™ 934 2.18 NaOH (50%) 5.74 Sodium Bo rate 0.99 Sodium Citrate3.96 Sodium Formate 1.98 CaCl 0.10 Sodium Xylene Sulfanate (40%) 4.95EO/PO Block Copolymer 1.98 Sodium Polyacrylate Mn1200 (45%) 9.89Protease 0.69 Amylase 0.20 Lemon Essential Oil 0.20 Total 100.0

Procedure: Combine and stir H₂O, citric acid and Bio-PDO™. Add Carbopol™to mixture and stir until dissolved. Slowly add NaOH, and thereafter addremaining ingredients.

Benefits: The resulting liquid dishwashing detergent displays very goodstability, enhanced rheology effects and less environmental inpact.

Example 57 Liquid Laundry Detergent

Ingredients Wt. % Linear Dodecyl Benzene Sulfonate 6.93 Coconut FattyAcid (C12-C18) 7.52 Tergitol 15-S-7 16.83 Triethanolamine 7.52 Bio-PDO ™(DuPont) 10.89 Citric Acid (50%) 6.33 KOH (45%) 9.30 Water 33.65Protease 0.69 Amylase 0.20 Lavendar Essential Oil 0.10 FD&C Blue 1 0.03FD&C Red 40 0.01 Total 100.0

Procedure: Combine Linear Dodecyl Benzene Sulfonate, H₂O,Triethanolamine and Bio-PDO™, and stir mixture at 70° C. Add Tergitol.Melt the fatty acids and add to the mix. Slowly add KOH, then slowly addthe citric acid. Cool mixture below 30° C. Add the enzymes, fragranceand dye.

Benefits: The resulting liquid laundry detergent exhibits very goodstability, exclellent cloud point and enhanced rheology effects.

Example 58 Liquid Laundry Detergent

Ingredients Wt. % C12-C13 Linear Alcohol EO-7 4.0 Linear Dodecyl BenzeneSulfonate (60%) 14.0 Sodium Laureth Sulfate (60%) 5.0 Sodium Citrate 4.0Sodium Borate 4.0 Bio-PDO ™ (DuPont) 3.0 Tinopal CBS-X 0.1 Protease 0.7Amylase 0.2 Monethanolamine 0.5 Coconut Fatty Acid (C12-C18) 2.0 Water62.5 Total 100.0

Physical Properties

pH, as is 8.5 Soluble Solids, 5 by refractometer 29.3 Residue on Drying,% by weight 28 Viscosity, cPs @ 25° C. 194 Visual Viscosity Water ThinFreeze/Thaw Stability −15°/25° C. Heat Stability (50° C.) 30 days

Example 59 Hand Dishwashing Liquid

Ingredients Wt. % Bio-PDO ™ (DuPont) 15.35 Linear Dodecyl BenzeneSulfonate 19.95 Triethanolamine 6.14 Cocamide DEA 10.74 Tergitol 15-S-74.60 Sodium Laureth-3EO Sulfate (28%) 4.60 Coco Amido Propyl Betaine7.67 Polyquaternium-6 (20%) 3.07 NaCl (25%) 1.53 Sodium Xylene Sulfanate(40%) 6.55 Water 19.19 Lemon Essential Oil 0.58 FD&C Yellow 5 0.03 FD&CRed 40 0.01 Total 100.0

Procedure: Combine all liquid ingredients and stir mixture at 70° C.Gradually add Linear Dodecyl Benzene Sulfonate and stir until dissolvedin mixture and mixture is clear. Cool mixture below 30° C. and addfragrance and coloring.

Benefits: The resulting hand dishwashing liquid exhibits very goodstability, improved foaming, excellent cloud point and requires lesssalt to adjust viscosity.

Example 60 Hand Dishwashing Liquid

Ingredients Wt. % Bio-PDO ™ (DuPont) 15.56 Linear Dodecyl BenzeneSulfonate 20.23 Triethanolamine 6.22 Cocamide DEA 10.89 Tergitol 15-S-74.67 Sodium Lauryl Sulfate 4.67 Coco Amido Propyl Betaine 7.78Polyquaternium-6 (20%) 3.11 NaCl (25%) 3.11 Sodium Xylene Sulfanate(40%) 3.50 Water 19.45 Lemon Essential Oil 0.78 FD&C Yellow 5 0.04 Total100.0

Procedure: Combine all liquid ingredients and stir mixture at 70° C.Gradually add Sodium Lauryl Sulfate and stir until dissolved and liquidmixture is clear. Gradually add Linear Dodecyl Benzene Sulfonate andstir until dissolved and liquid mixture is clear. Cool mixture below 30°C. and add fragrance and coloring.

Example 61 Detergents Comprising Esters Formed from Biologically Derived1,3-Propanediol

Fatty acid glycol ester (e.g., Monoethylene glycol distearate)5.0-30.0%; Fatty acid alkanolamide (e.g., Coconut oil acidmonoethanolamide) 2.0-20.0%; Surfactant (e.g., Sodium lauryl triglycolether-sulfosuccinate or Coconut-alkyldimethylamine oxide) 0.1-10.0%;Sodium salt (e.g., Mono- or Di-valent) 0.1-3.0%; and water up to 100%.

Addition of a fatty acid glycol ester with a fatty acid alkanolamide andan ether-sulfate-free surfactant will yield a pearlescent dispersionhaving 1) excellent pearlescent effect, 2) good storage ability, and 3)low viscosity. This composition will form a pearlescent dispersion withgood flow properties and low surfactant content.

Example 62 Liquid Detergent Comprising Esters Formed from BiologicallyDerived 1,3-Propanediol

Fatty acid glycol ester (e.g., Monoethylene glycol distearate)5.0-30.0%; Fatty acid alkanolamide (e.g., Cocomonoethanolamide)2.0-20.0%; Nonionic surfactant (e.g., C₁₀-C₁₂-Fatty polyol alkyl ester)0.1-10.0%; water up to 100%.

Addition of a fatty acid glycol ester with a fatty acid alkanolamide anda nonionic surfactant will yield a pearlescent dispersion having 1)excellent pearl luster effect, 2) long shelf life, 3) compatibility withcationic surfactants, 4) resistance to hydrolysis, 5) low viscosity, and6) reduced foaming.

Example 63 Liquid Detergent Comprising Esters Formed from BiologicallyDerived 1,3-Propanediol

Fatty acid glycol ester (e.g., Ethylene glycol distearate) 5.0-40.0%;Nonionic surfactant (e.g., Laureth-7) 3.0-30.0%; Amphoteric surfactant(e.g., Cocoamidopropyl betaine and Cocoamphoacetate) 0.0-10.0%; Glycol(e.g., Propylene glycol (1,2 and 1,3) 0.0-15.0%; water up to 100%.

Uses: 1) fatty acid glycol ester=pearlizing agent, 2) nonionicsurfactant=emulsifier and stabilizer, 3) amphotericsurfactant=co-emulsifier to enhance pearlizing effect, and 4)glycol=emulsifier.

Example 64 Liquid Detergent Comprising Esters Formed from BiologicallyDerived 1,3-Propanediol

Fatty acid glycol ester sulfate (A) (e.g., Lauric acid (ethylene glycol)sulfate sodium salt) 10.0-60.0%; Additional surfactant (B) (anionic,nonionic, cationic, amphoteric, and/or zwitterionic) (e.g., Sodiumlaureth sulfate) 90.0-40.0%; water up to 100.0%.

Foaming behavior may be tested by, preparing a 10% by weight aqueoussurfactant solution (21° dH+1% by weight sebum) and determining the foamvolume by Standard DIN 53902, Part 1. Test solutions can be made usingweight ratios of A (10.0-60.0%) and B (90.0-40.0%). The fatty acidglycol ester sulfates may exhibit advantageous properties: 1) foambooster for other surfactants, 2) foam stability in the presence of hardwater and/or oil, 3) improve formulation of surfactants with poorsolubility in cold water, 4) contribute to cleaning performance, 5)dermatologically safe, 6) readily biodegradable, and 7) free ofnitosamines.

Example 65 Liquid Detergent Comprising Esters Formed from BiologicallyDerived 1,3-Propanediol

Surfactant (anionic, nonionic, or amphoteric) (e.g., Sodium POE (3)lauryl ether sulfate, Lauryl amidopropylbetaine, Coconut oil fatty acidmonothanol amide, and POE (12) lauryl ether) 1.0-50.0%; Fatty acidglycol ester (e.g., Ethylene glycol distearate) 0.3-5.0%; Glyceryl ether(e.g., N-Octyl glyceryl ether) 0.1-10.0%; water up to 100%.

Compositions will have 1) a pearly luster, and 2) are excellent in thedispersion stability of a pearlent.

Procedure—combine all ingredients together, heating the mixture to 80°C. and allowing the ingredients to melt, and then cooling the melt to30° C. with stirring.

Example 66 Liquid Detergent Comprising Esters Formed from BiologicallyDerived 1,3-Propanediol

Diamine (pKa1 & pKa2 range 8.0-11.5 and molecular weight less-than orequal-to 400 g/mol) (e.g., 1,3-bis(methylamine)-cyclohexane) 0.1-15.0%;Anionic Surfactant (e.g., C₁₂-C₁₃ alkyl ethoxy sulfonate) 0.5-90.0%;Amphoteric Surfactant (e.g., C₁₂-C₁₄ amine oxide) 0.10-20.0%; Glycol(e.g., Propylene Glycol) 0.75-25.0%; Optional Ingredients includePolymeric Suds Stabilizer (e.g., (N,N,-dimethylamino)ethyl methacrylate)0.01-15.0%; Builder (e.g., Citric Acid) 0.50-50.0%; Enzyme(s) (e.g.,Alcalase® (Novo Industri A/S) and TERMAMYL® (Novo Industri A/S))0.0001-5.0%; Buffer (e.g., Sodium Carbonate) 0.10-10.0%; AlkaliInorganic Salt (e.g., NaCl) 0.01-1.0%: Perfume (e.g., Orange Oil)0.01-2.0%; Chelating Agents (e.g., Ethylenediaminetetrace-tates)0.01-15.0%.

Diamines—Improve cleaning performance; Surfactants—Cleaning performance;Glycols—1) Enhanced physical and enzymatic stability, 2) Act as ahydrotrope (phase stabilizer); Suds Stabilizer—Extend suds volume andduration; Builder—Support detergent action; Enzyme—Cleaning performance;Buffer—pH adjustment; Alkali Inorganic Salt—Support detergent action;Perfume—Help remove iron and manganese.

What is claimed:
 1. A flavoring agent composition comprising an ester of1,3-propanediol, wherein the composition is biodegradable, wherein theester is a monomer and comprises at least 3% biobased carbon, andwherein said composition has a lower anthropogenic CO₂ emission profileas compared to a biodegradable composition comprising an ester of1,3-propanediol with a bio-based carbon content of 0%.
 2. Thecomposition of claim 1, wherein the flavoring agent composition furthercomprises a flavoring oil.
 3. The composition of claim 2 wherein theflavoring oil comprises orange oil.
 4. The composition of claim 1,wherein the ester has 50% biobased carbon.
 5. The composition of claim1, wherein the ester has 100% biobased carbon.
 6. The composition ofclaim 1, wherein the ester has the formula R1-C(═O)—O—CH2-CH2-CH2-OH,wherein R1 is a linear or branched carbon chain of a length betweenabout 1 and about 40 carbons.
 7. The composition of claim 1, wherein theester has the formula R1-C(═O)—O—CH2-CH2-CH2-O—C(═O)—R2, wherein R1 andR2 are linear or branched carbon chains of a length between about 1 andabout 40 carbons.
 8. The composition of claim 1, wherein the ester isselected from the group consisting of: i. propanediol distearate,monostearate and a mixture thereof; ii. propandiol dilaurate,monolaurate and a mixture thereof; iii. propanediol dioleate, monooleateand a mixture thereof; iv. propanediol divalerate, monovalerate and amixture thereof; v. propanediol dicaprylate, monocaprylate and a mixturethereof; vi. propanediol dimyristate, monomyristate and a mixturethereof; vii. propanediol dipalmitate, monopalmitate and a mixturethereof; viii. propanediol dibehenate, monobehenate and a mixturethereof; ix. propanediol adipate; x. propanediol maleate; xi.propanediol dibenzoate; xii. propanediol diacetate; and xiii. mixturesthereof.
 9. The composition of claim 1, further comprising1,3-propanediol.
 10. The composition of claim 9, wherein the1,3-propanediol has 50% biobased carbon.
 11. The composition of claim 9,wherein the 1,3-propanediol has 100% biobased carbon.
 12. A flavoringagent composition comprising 1,3-propanediol, wherein the1,3-propanediol is biologically derived, wherein the composition isbiodegradable and has a lower anthropogenic CO₂ emission profile ascompared to a biodegradable composition comprising 1,3-propanediol witha bio-based carbon content of 0%, and wherein the 1,3-propanediol is amonomer, and comprises at least 3% biobased carbon.
 13. The compositionof claim 12, wherein the flavoring agent composition further comprises aflavoring oil.
 14. The composition of claim 13 wherein the flavoring oilcomprises orange oil.
 15. The composition of claim 12, wherein the1,3-propanediol has 50% biobased carbon.
 16. The composition of claim12, wherein the 1,3-propanediol has 100% biobased carbon.
 17. A food,pharmaceutical or medicine composition comprising the composition ofclaim
 1. 18. A food, pharmaceutical or medicine composition comprisingthe composition of claim 12.